Aryloxypyrimidinyl ethers as herbicides

ABSTRACT

Also disclosed are compositions containing the compounds of Formula 1 and methods for controlling undesired vegetation comprising contacting the undesired vegetation or its environment with an effective amount of a compound or a composition of the invention.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is the national stage entry of International Application No. PCT/US2016/041444, filed on Jul. 8, 2016, which claims priority to U.S. Provisional Application No. 62/191,560, filed on Jul. 13, 2015, the contents of which are incorporated by reference in their entirety herein.

FIELD OF THE INVENTION

This disclosure relates to certain aryloxypyrimidinyl ethers, their N-oxides, salts and compositions, and methods of their use for controlling undesirable vegetation.

BACKGROUND OF THE INVENTION

The control of undesired vegetation is extremely important in achieving high crop efficiency. Achievement of selective control of the growth of weeds especially in such useful crops as rice, soybean, sugar beet, maize, potato, wheat, barley, tomato and plantation crops, among others, is very desirable. Unchecked weed growth in such useful crops can cause significant reduction in productivity and thereby result in increased costs to the consumer. The control of undesired vegetation in noncrop areas is also important. Many products are commercially available for these purposes, but the need continues for new compounds that are more effective, less costly, less toxic, environmentally safer or have different sites of action.

SUMMARY OF THE INVENTION

This invention is directed to compounds of Formula 1 (including all stereoisomers), (N-oxides, and salts thereof), agricultural compositions containing them and their use as herbicides:

wherein

-   -   A is C₂-C₈ alkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl, C₂-C₈ haloalkyl,         C₂-C₆ haloalkenyl, C₂-C₆ haloalkynyl, C₃-C₆ cycloalkyl, C₃-C₆         halocycloalkyl, C₄-C₈ alkylcycloalkyl, C₄-C₈ cycloalkylalkyl,         C₂-C₆ alkoxyalkyl, C₂-C₆ haloalkoxyalkyl, C₂-C₆ alkoxyhaloalkyl,         C₄-C₈ cycloalkoxyalkyl, C₂-C₆ cyanoalkyl, C₃-C₇         cyanoalkoxyalkyl, C₁-C₆ nitroalkyl, C₂-C₆ alkylthioalkyl, C₂-C₆         haloalkylthioalkyl, C₃-C₈ cycloalkylthioalkyl, C₂-C₆         alkylsulfinylalkyl, C₂-C₆ haloalkylsulfinylalkyl, C₂-C₆         alkylsulfonylalkyl, C₂-C₆ haloalkylsulfonylalkyl, C₂-C₆         alkylcarbonyl, C₂-C₆ haloalkylcarbonyl, C₂-C₆         alkylcarbonylalkyl, C₂-C₆ haloalkylcarbonylalkyl, C₂-C₆         alkoxycarbonylalkyl, C₂-C₆ haloalkoxycarbonylalkyl or C₂-C₆         alkoxyalkylcarbonyl; or G; or C₁-C₄ alkyl substituted with Q;     -   R¹ is halogen, C₁-C₄ alkyl, C₁-C₄ haloalkyl, C₂-C₆ alkenyl,         C₂-C₆ alkynyl, C₁-C₄ alkoxy or S(O)_(n)R⁴;     -   R² is halogen, cyano, nitro, CHO, C(═O)NH₂, C(═S)NH₂, SO₂NH₂,         C₁-C₄ alkyl, C₂-C₄ alkenyl, C₂-C₄ alkynyl, C₁-C₄ haloalkyl,         C₂-C₄ haloalkenyl, C₂-C₄ haloalkynyl, C₃-C₆ cycloalkyl, C₃-C₆         halocycloalkyl, C₄-C₈ alkylcycloalkyl, C₄-C₈ cycloalkylalkyl,         C₂-C₆ alkylcarbonyl, C₂-C₆ haloalkylcarbonyl, C₂-C₆         alkoxycarbonyl, C₃-C₇ cycloalkylcarbonyl, C₂-C₄ alkoxy, C₃-C₄         alkenyloxy, C₃-C₄ alkynyloxy, C₁-C₄ haloalkoxy, C₃-C₆         cycloalkoxy, C₃-C₆ halocycloalkoxy, C₄-C₈ cycloalkylalkoxy,         C₂-C₆ alkoxyalkyl, C₂-C₆ haloalkoxyalkyl, C₂-C₆ alkoxyhaloalkyl,         C₂-C₆ alkoxyalkoxy, C₂-C₄ alkylcarbonyloxy, C₂-C₆ cyanoalkyl,         C₂-C₆ cyanoalkoxy, C₂-C₄ alkylthioalkyl, C(═O)N(R^(5a))(R^(5b)),         C(═NOR⁶)H, C(═NR⁷)H or SO_(n)R⁴;     -   R³ is H or F;     -   G is a 3- to 7-membered nonaromatic heterocyclic ring containing         ring members selected from carbon, up to 4 heteroatoms selected         from up to 2 O up to 2 S and up to 4 N, and up to 3 ring members         selected from C(═O), C(═S) and S(═O)_(a)(═NR⁶)_(b) and         substituted with up to 3 substituents independently selected         from halogen, cyano, C₁-C₄ alkyl, C₁-C₄ haloalkyl, C₁-C₄ alkoxy         or C₁-C₄ haloalkoxy;     -   Q is a phenyl ring optionally substituted with up to 5         substituents independently selected from R⁸; or a 5- or         6-membered heteroaromatic ring containing ring members selected         from carbon atoms and up to 4 heteroatoms independently selected         from up to 2 O up to 2 S and up to 4 N atoms and optionally         substituted with up to 3 substituents independently selected         from R^(9a) on carbon atom ring members and R^(9b) on nitrogen         atom ring members;     -   each R⁴ is independently C₁-C₆ alkyl or C₁-C₆ haloalkyl;     -   each R^(5a) is independently C₁-C₄ alkyl or C₁-C₄ haloalkyl;     -   each R^(5b) is independently H, C₁-C₄ alkyl or C₁-C₄ haloalkyl;     -   each R⁶ is independently H or C₁-C₄ alkyl;     -   each R⁷ is independently H, amino, C₁-C₄ alkyl or C₁-C₄         alkylamino;     -   each R⁸ is independently halogen, cyano, C₁-C₄ alkyl, C₁-C₄         haloalkyl, C₁-C₄ alkoxy or C₁-C₄ haloalkoxy;     -   each R^(9a) is independently halogen, cyano, C₁-C₄ alkyl, C₁-C₄         haloalkyl, C₁-C₄ alkoxy or C₁-C₄ haloalkoxy;     -   each R^(9b) is independently H, C₁-C₃ alkyl, C₁-C₃         alkylcarbonyl, C₁-C₃ alkoxy or C₁-C₃ alkoxycarbonyl;     -   each n is independently 0, 1 or 2; and     -   a and b are independently 0, 1 or 2, provided that the sum of a         and b is 1 or 2; and     -   provided that when R¹ is Cl; R³ is H; and A is —C(═O)CH₂CH₂CF₃;         then R² is other than Br or cyano.

More particularly, this invention pertains to a compound of Formula 1 (including all stereoisomers), an N-oxide or a salt thereof. This invention also relates to a herbicidal composition comprising a compound of the invention (i.e. in a herbicidally effective amount) and at least one component selected from the group consisting of surfactants, solid diluents and liquid diluents. This invention further relates to a method for controlling the growth of undesired vegetation comprising contacting the vegetation or its environment with a herbicidally effective amount of a compound of the invention (e.g., as a composition described herein).

This invention also includes a herbicidal mixture comprising (a) a compound selected from Formula 1, N-oxides, and salts thereof, and (b) at least one additional active ingredient selected from (b1) through (b16); and salts of compounds of (b1) through (b16), as described below.

DETAILS OF THE INVENTION

As used herein, the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having,” “contains”, “containing,” “characterized by” or any other variation thereof, are intended to cover a non-exclusive inclusion, subject to any limitation explicitly indicated. For example, a composition, mixture, process or method that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, mixture, process or method.

The transitional phrase “consisting of” excludes any element, step, or ingredient not specified. If in the claim, such would close the claim to the inclusion of materials other than those recited except for impurities ordinarily associated therewith. When the phrase “consisting of” appears in a clause of the body of a claim, rather than immediately following the preamble, it limits only the element set forth in that clause; other elements are not excluded from the claim as a whole.

The transitional phrase “consisting essentially of” is used to define a composition or method that includes materials, steps, features, components, or elements, in addition to those literally disclosed, provided that these additional materials, steps, features, components, or elements do not materially affect the basic and novel characteristic(s) of the claimed invention. The term “consisting essentially of” occupies a middle ground between “comprising” and “consisting of”.

Where applicants have defined an invention or a portion thereof with an open-ended term such as “comprising,” it should be readily understood that (unless otherwise stated) the description should be interpreted to also describe such an invention using the terms “consisting essentially of” or “consisting of.”

Further, unless expressly stated to the contrary, “or” refers to an inclusive or and not to an exclusive or. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).

Also, the indefinite articles “a” and “an” preceding an element or component of the invention are intended to be nonrestrictive regarding the number of instances (i.e. occurrences) of the element or component. Therefore “a” or “an” should be read to include one or at least one, and the singular word form of the element or component also includes the plural unless the number is obviously meant to be singular.

As referred to herein, the term “seedling”, used either alone or in a combination of words means a young plant developing from the embryo of a seed.

As referred to herein, the term “broadleaf” used either alone or in words such as “broadleaf weed” means dicot or dicotyledon, a term used to describe a group of angiosperms characterized by embryos having two cotyledons.

As used herein, the term “alkylating agent” refers to a chemical compound in which a carbon-containing radical is bound through a carbon atom to a leaving group such as halide or sulfonate, which is displaceable by bonding of a nucleophile to said carbon atom. Unless otherwise indicated, the term “alkylating” does not limit the carbon-containing radical to alkyl; the carbon-containing radicals in alkylating agents include the variety of carbon-bound substituent radicals specified for A.

In the above recitations, the term “alkyl”, used either alone or in compound words such as “alkylthio” or “haloalkyl” includes straight-chain or branched alkyl, such as, methyl, ethyl, n-propyl, i-propyl, or the different butyl, pentyl or hexyl isomers. “Alkenyl” includes straight-chain or branched alkenes such as ethenyl, 1-propenyl, 2-propenyl, and the different butenyl, pentenyl and hexenyl isomers. “Alkenyl” also includes polyenes such as 1,2-propadienyl and 2,4-hexadienyl. “Alkynyl” includes straight-chain or branched alkynes such as ethynyl, 1-propynyl, 2-propynyl and the different butynyl, pentynyl and hexynyl isomers. “Alkynyl” can also include moieties comprised of multiple triple bonds such as 2,5-hexadiynyl.

“Alkoxy” includes, for example, methoxy, ethoxy, n-propyloxy, isopropyloxy and the different butoxy, pentoxy and hexyloxy isomers. “Alkoxyalkyl” denotes alkoxy substitution on alkyl. Examples of “alkoxyalkyl” include CH₃OCH₂, CH₃OCH₂CH₂, CH₃CH₂OCH₂, CH₃CH₂CH₂CH₂OCH₂ and CH₃CH₂OCH₂CH₂. “Alkoxyalkoxy” denotes alkoxy substitution on alkoxy. “Alkenyloxy” includes straight-chain or branched alkenyloxy moieties. Examples of “alkenyloxy” include H₂C═CHCH₂O, (CH₃)₂C═CHCH₂O, (CH₃)CH═CHCH₂O, (CH₃)CH═C(CH₃)CH₂O and CH₂═CHCH₂CH₂O. “Alkynyloxy” includes straight-chain or branched alkynyloxy moieties. Examples of “alkynyloxy” include HC≡CCH₂O, CH₃C≡CCH₂O and CH₃C≡CCH₂CH₂O. “Alkylthio” includes branched or straight-chain alkylthio moieties such as methylthio, ethylthio, and the different propylthio, butylthio, pentylthio and hexylthio isomers. “Alkylsulfinyl” includes both enantiomers of an alkylsulfinyl group. Examples of “alkylsulfinyl” include CH₃S(O)—, CH₃CH₂S(O)—, CH₃CH₂CH₂S(O)—, (CH₃)₂CHS(O)— and the different butylsulfinyl, pentylsulfinyl and hexylsulfinyl isomers. Examples of “alkylsulfonyl” include CH₃S(O)₂—, CH₃CH₂S(O)₂—, CH₃CH₂CH₂S(O)₂—, (CH₃)₂CHS(O)₂—, and the different butylsulfonyl, pentylsulfonyl and hexylsulfonyl isomers. “Alkylthioalkyl” denotes alkylthio substitution on alkyl. Examples of “alkylthioalkyl” include CH₃SCH₂—, CH₃SCH₂CH₂—, CH₃CH₂SCH₂—, CH₃CH₂CH₂CH₂SCH₂— and CH₃CH₂SCH₂CH₂—. “Alkylamino”, “dialkylamino”, “alkenylthio”, “alkenylsulfinyl”, “alkenylsulfonyl”, “alkynylthio”, “alkynylsulfinyl”, “alkynylsulfonyl”, “alkylsulfinylalkyl”, “alkysulfonylalkyl” and the like, are defined analogously to the above examples. “Cyanoalkyl” denotes an alkyl group substituted with one cyano group. Examples of “cyanoalkyl” include NCCH₂, NCCH₂CH₂ and CH₃CH(CN)CH₂. “Cyanoalkoxy” denotes an alkoxy group substituted with one cyano group. Examples of “cyanoalkoxy” include NCCH₂O, NCCH₂CH₂O and CH₃CH(CN)CH₂O. “Cyanoalkoxyalkyl” denotes an alkoxyalkyl group substituted with one cyano group. Examples of “cyanoalkoxyalkyl” include NCCH₂OCH₂, NCCH₂CH₂OCH₂ and CH₃CH(CN)CH₂OCH₂. “Nitroalkyl” denotes an alkyl group substituted with one nitro group. Examples of “nitroalkyl” include O₂NCH₂, O₂NCH₂CH₂ and CH₃CH(NO₂)CH₂.

“Cycloalkyl” includes, for example, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. The term “alkylcycloalkyl” denotes alkyl substitution on a cycloalkyl moiety and includes, for example, ethylcyclopropyl, i-propylcyclobutyl, 3-methylcyclopentyl and 4-methylcyclohexyl. The term “cycloalkylalkyl” denotes cycloalkyl substitution on an alkyl moiety. Examples of “cycloalkylalkyl” include cyclopropylmethyl, cyclopentylethyl, and other cycloalkyl moieties bonded through straight-chain or branched alkyl groups. The term “alkylcycloalkyl” denotes alkyl substitution on a cycloalkyl moiety. Examples of “alkylcycloalkyl” include methylcyclopropyl, ethylcyclopentyl, and other alkyl moieties bonded to a cycloalkyl group. The term “cycloalkoxy” denotes cycloalkyl linked through an oxygen atom such as cyclopentyloxy and cyclohexyloxy. The term “cycloalkylcarbonyl” denotes cycloalkyl linked through a carbonyl moiety. The term “cycloalkoxyalkyl” denotes a cycloalkoxy group linked through an alkyl group such as cyclopentyloxymethyl and cyclohexyloxyethyl. The term “cycloalkylthioalkyl” denotes cycloalkylthio moiety linked through an alkyl group. “Cycloalkylalkoxy” denotes a cycloalkyl moiety linked through an alkoxy group. Examples of “cycloalkylalkoxy” include cyclopropylmethoxy, cyclopentylethoxy, and other cycloalkyl moieties bonded to straight-chain or branched alkoxy groups.

The term “halogen”, either alone or in compound words such as “haloalkyl”, or when used in descriptions such as “alkyl substituted with halogen” includes fluorine, chlorine, bromine or iodine. Further, when used in compound words such as “haloalkyl”, or when used in descriptions such as “alkyl substituted with halogen” said alkyl may be partially or fully substituted with halogen atoms which may be the same or different. Examples of “haloalkyl” or “alkyl substituted with halogen” include F₃C, ClCH₂, CF₃CH₂ and CF₃CCl₂. The terms “halocycloalkyl”, “haloalkoxy”, “haloalkoxyalkyl”, “haloalkoxyalkoxy”, “haloalkylcarbonyl”, “haloalkylcarbonylalkyl”, “haloalkoxycarbonylalkyl”, “alkoxyhaloalkyl”, “haloalkylthio”, “haloalkylthioalkyl”, “haloalkylsulfinyl”, “haloalkylsulfinylalkyl”, “haloalkylsulfonyl”, “haloalkylsulfonylalkyl”, “haloalkenyl”, “haloalkynyl”, and the like, are defined analogously to the term “haloalkyl”. Examples of “halocycloalkyl” include c-Pr(1-Cl)—, c-Bu(2-Br)— and c-hex(4-Cl)—. Examples of “haloalkoxy” include CF₃O—, CCl₃CH₂O—, HCF₂CH₂CH₂O— and CF₃CH₂O—. Examples of “haloalkoxyalkyl” include CF₃OCH—, CF₃CH₂OCH₂CH₂—, CH₂ClCH₂OCH₂— as well as branched haloalkoxy derivatives. Examples of “haloalkoxyalkoxy” include CF₃OCH₂O—, ClCH₂CH₂OCH₂CH₂O—, Cl₃CCH₂OCH₂O— as well as branched alkyl derivatives. Examples of “haloalkylcarbonyl” include CF₃C(═O)—, CF₃CH₂C(═O)— and CF₃CF₂C(═O)—. Examples of “haloalkylcarbonylalkyl” include CF₃C(═O)CH₂—, CF₃CH₂C(═O)CH₂— and CF₃CF₂C(═O)CH₂—. Examples of “haloalkoxycarbonylalkyl” include CF₃OC(═O)CH₂—, CF₃CH₂OC(═O)CH₂— and CF₃CF₂OC(═O)CH₂—. Examples of “alkoxyhaloalkyl” include CH₃OCHF—, CH₃CH₂OCF₂CH₂—, CH₃CH₂OCCl₂— as well as branched alkoxy derivatives. Examples of “haloalkylthio” include CCl₃S—, CF₃S—, CCl₃CH₂S— and ClCH₂CH₂CH₂S—. Examples of “haloalkylthioalkyl” include CCl₃SCH₂—, CF₃SCH₂—, CCl₃CH₂SCH₂— and ClCH₂CH₂CH₂SCH₂—. Examples of “haloalkylsulfinyl” include CF₃S(O)—, CCl₃S(O)—, CF₃CH₂S(O)— and CF₃CF₂S(O)—. Examples of “haloalkylsulfinylalkyl” include CF₃S(O)CH₂—, CCl₃S(O)CH₂—, CF₃CH₂S(O)CH₂— and CF₃CF₂S(O)CH₂—. Examples of “haloalkylsulfonyl” include CF₃S(O)₂—, CCl₃S(O)₂—, CF₃CH₂S(O)₂— and CF₃CF₂S(O)₂—. Examples of “haloalkylsulfonylalkyl” include CF₃S(O)₂CH₂—, CCl₃S(O)₂CH₂—, CF₃CH₂S(O)₂CH₂— and CF₃CF₂S(O)₂CH₂—. Examples of “haloalkenyl” include (Cl)₂C═CHCH₂— and CF₃CH₂CH═CHCH₂—. Examples of “haloalkynyl” include HC≡CCHCl—, CF₃C≡C—, CCl₃C≡C— and FCH₂C≡CCH₂—.

“Alkylcarbonyl” denotes a straight-chain or branched alkyl moiety bonded to a C(═O) moiety. Examples of “alkylcarbonyl” include CH₃C(═O)—, CH₃CH₂CH₂C(═O)— and (CH₃)₂CHC(═O)—. “Alkoxycarbonyl” denotes a straight-chain or branched alkoxy moiety bonded to a C(═O) moiety. Examples of “alkoxycarbonyl” include CH₃OC(═O)—, CH₃CH₂OC(═O)—, CH₃CH₂CH₂OC(═O)—, (CH₃)₂CHOC(═O)— and the different butoxy- or pentoxycarbonyl isomers. “Alkoxyalkylcarbonyl” denotes a straight-chain or branched alkoxyalkyl moiety bonded to a C(═O) moiety. Examples of “alkoxyalkylcarbonyl” include CH₃OCH₂CH₂C(═O)— and CH₃CH₂OCH₂C(═O)—. “Alkoxycarbonylalkyl” denotes a straight-chain or branched alkoxycarbonyl moiety bonded through alkyl. Examples of “alkoxycarbonylalkyl” include CH₃OC(═O)CH₂—, CH₃CH₂CH₂OC(═O)CH₂— and (CH₃)₂CHCO(═O)CH₂—. “Alkylcarbonylalkyl” denotes a straight-chain or branched alkyl moiety bonded to a carbonylalkyl group. Examples of “alkylcarbonylalkyl” include CH₃CH₂CH₂C(═O)CH₂— and CH₃CH₂CH₂C(═O)CH₂—. “Alkylcarbonyloxy” denotes a straight-chain or branched alkyl moiety bonded to a carbonylalkyl group. Examples of “Alkylcarbonyloxy” include CH₃CH₂CH₂C(═O)O— and CH₃CH₂CH₂C(═O)O—.

The total number of carbon atoms in a substituent group is indicated by the “C_(i)-C_(j)” prefix where i and j are numbers from 1 to 8. For example, C₁-C₄ alkylsulfonyl designates methylsulfonyl through butylsulfonyl; C₂ alkoxyalkyl designates CH₃OCH₂—; C₃ alkoxyalkyl designates, for example, CH₃CH(OCH₃)—, CH₃OCH₂CH₂— or CH₃CH₂OCH₂—; and C₄ alkoxyalkyl designates the various isomers of an alkyl group substituted with an alkoxy group containing a total of four carbon atoms, examples including CH₃CH₂CH₂OCH₂— and CH₃CH₂OCH₂CH₂—.

When a group contains a substituent which can be hydrogen, for example R³, then when this substituent is taken as hydrogen, it is recognized that this is equivalent to said group being unsubstituted. When a variable group is shown to be optionally attached to a position, for example [(R^(v))_(r)] wherein r may be 0, then hydrogen may be at the position even if not recited in the variable group definition. When one or more positions on a group are said to be “not substituted” or “unsubstituted”, then hydrogen atoms are attached to take up any free valency.

Unless otherwise indicated, a “ring” as a component of Formula 1 (e.g., substituent Q) is carbocyclic or heterocyclic. The term “ring member” refers to an atom or other moiety (e.g., C(═O), C(═S), S(O) or S(O)₂) forming the backbone of a ring. The term “carbocyclic ring” denotes a ring or ring system wherein the atoms forming the ring backbone are selected only from carbon. Unless otherwise indicated, a carbocyclic ring can be a saturated, partially unsaturated, or fully unsaturated ring. When a fully unsaturated carbocyclic ring satisfies Hückey's rule, then said ring is also called an “aromatic ring”. “Saturated carbocyclic” refers to a ring having a backbone consisting of carbon atoms linked to one another by single bonds; unless otherwise specified, the remaining carbon valences are occupied by hydrogen atoms.

The term “heterocyclic ring” denotes a ring in which at least one atom forming the ring backbone is not carbon, e.g., nitrogen, oxygen or sulfur. Typically a heterocyclic ring contains no more than 4 nitrogens, no more than 2 oxygens and no more than 2 sulfurs. Unless otherwise indicated, a heterocyclic ring can be a saturated, partially unsaturated, or fully unsaturated ring. When a fully unsaturated heterocyclic ring satisfies Hückel's rule, then said ring is also called a “heteroaromatic ring” or “aromatic heterocyclic ring”. Unless otherwise indicated, heterocyclic rings can be attached through any available carbon or nitrogen by replacement of a hydrogen on said carbon or nitrogen.

“Aromatic” indicates that each of the ring atoms is essentially in the same plane and has a p-orbital perpendicular to the ring plane, and that (4n+2) π electrons, where n is a positive integer, are associated with the ring to comply with Hückel's rule. The term “aromatic carbocyclic ring system” denotes a carbocyclic ring system in which at least one ring of the ring system is aromatic. The term “aromatic heterocyclic ring system” denotes a heterocyclic ring system in which at least one ring of the ring system is aromatic. The term “nonaromatic ring system” denotes a carbocyclic or heterocyclic ring system that may be fully saturated, as well as partially or fully unsaturated, provided that none of the rings in the ring system are aromatic. The term “nonaromatic carbocyclic ring system” in which no ring in the ring system is aromatic. The term “nonaromatic heterocyclic ring system” denotes a heterocyclic ring system in which no ring in the ring system is aromatic.

The term “optionally substituted” in connection with the heterocyclic rings refers to groups which are unsubstituted or have at least one non-hydrogen substituent that does not extinguish the biological activity possessed by the unsubstituted analog. As used herein, the following definitions shall apply unless otherwise indicated. The term “optionally substituted” is used interchangeably with the phrase “substituted or unsubstituted” or with the term “(un)substituted.” Unless otherwise indicated, an optionally substituted group may have a substituent at each substitutable position of the group, and each substitution is independent of the other.

When Q is a 5- or 6-membered nitrogen-containing heterocyclic ring, it may be attached to the remainder of Formula 1 though any available carbon or nitrogen ring atom, unless otherwise described. As noted above, Q can be (among others) phenyl optionally substituted with one or more substituents selected from a group of substituents as defined in the Summary of the Invention. An example of phenyl optionally substituted with one to five substituents is the ring illustrated as U-1 in Exhibit 1, wherein R^(v) is R⁸ as defined in the Summary of the Invention for Q and r is an integer from 0 to 5.

As noted above, Q can be (among others) 5- or 6-membered heteroaromatic, which may be saturated or unsaturated, optionally substituted with one or more substituents selected from a group of substituents as defined in the Summary of the Invention. Examples of a 5- or 6-membered unsaturated heteroaromatic ring optionally substituted with from one or more substituents include the rings U-2 through U-61 illustrated in Exhibit 1 wherein R^(v) is any substituent as defined in the Summary of the Invention for Q (i.e. R^(9a) or R^(9b)) and r is an integer from 0 to 3, limited by the number of available positions on each U group. As U-29, U-30, U-36, U-37, U-38, U-39, U-40, U-41, U-42 and U-43 have only one available position, for these U groups r is limited to the integers 0 or 1, and r being 0 means that the U group is unsubstituted and a hydrogen is present at the position indicated by (R^(v))_(r).

Exhibit 1

When A is “C₁-C₄ alkyl substituted with Q”, it is understood that Q is linked through a linear or branched alkyl moiety (i.e. alkylene) with the remainder of Formula 1. Examples of A being “C₁-C₄ alkyl substituted with Q” include —CH₂Q, —CH₂CH₂Q and —CH₂CH(CH₃)Q. Note that when G is, among others, a 5- or 6-membered saturated or unsaturated non-aromatic heterocyclic ring optionally substituted with one or more substituents selected from the group of substituents as defined in the Summary of the Invention for G, one or two carbon ring members of the heterocycle can optionally be in the oxidized form of a carbonyl moiety.

Examples of a 5- or 6-membered saturated or non-aromatic unsaturated heterocyclic ring (e.g., when G is a subset of “a 3- to 7-membered nonaromatic heterocyclic ring”) containing ring members selected from up to two O atoms and up to two S atoms, and optionally substituted on carbon atom ring members with up to 3 substiutents as defined in the Summary of the Invention includes the rings G-1 through G-35 as illustrated in Exhibit 2. Note that when the attachment point on the G group is illustrated as floating, the G group can be attached to the remainder of Formula 1 through any available carbon or nitrogen of the G group by replacement of a hydrogen atom. The optional substituents corresponding to R^(v) can be attached to any available carbon or nitrogen by replacing a hydrogen atom. For these G rings, r is typically an integer from 0 to 3, limited by the number of available positions on each G group.

Note that when G comprises a ring selected from G-28 through G-35, G² is selected from O, S or N. Note that when G² is N, the nitrogen atom can complete its valence by substitution with either H or the substituents as defined in the Summary of the Invention.

Exhibit 2

A wide variety of synthetic methods are known in the art to enable preparation of aromatic and nonaromatic heterocyclic rings and ring systems; for extensive reviews see the eight volume set of Comprehensive Heterocyclic Chemistry, A. R. Katritzky and C. W. Rees editors-in-chief, Pergamon Press, Oxford, 1984 and the twelve volume set of Comprehensive Heterocyclic Chemistry II, A. R. Katritzky, C. W. Rees and E. F. V. Scriven editors-in-chief, Pergamon Press, Oxford, 1996.

Compounds of this invention can exist as one or more stereoisomers. The various stereoisomers include enantiomers, diastereomers, atropisomers and geometric isomers. Stereoisomers are isomers of identical constitution but differing in the arrangement of their atoms in space and include enantiomers, diastereomers, cis-trans isomers (also known as geometric isomers) and atropisomers. Atropisomers result from restricted rotation about single bonds where the rotational barrier is high enough to permit isolation of the isomeric species. One skilled in the art will appreciate that one stereoisomer may be more active and/or may exhibit beneficial effects when enriched relative to the other stereoisomer(s) or when separated from the other stereoisomer(s). Additionally, the skilled artisan knows how to separate, enrich, and/or to selectively prepare said stereoisomers. The compounds of the invention may be present as a mixture of stereoisomers, individual stereoisomers or as an optically active form. For a comprehensive discussion of all aspects of stereoisomerism, see Ernest L. Eliel and Samuel H. Wilen, Stereochemistry of Organic Compounds, John Wiley & Sons, 1994.

Compounds of Formula 1 typically exist in more than one form, and Formula 1 thus include all crystalline and non-crystalline forms of the compounds they represent. Non-crystalline forms include embodiments which are solids such as waxes and gums as well as embodiments which are liquids such as solutions and melts. Crystalline forms include embodiments which represent essentially a single crystal type and embodiments which represent a mixture of polymorphs (i.e. different crystalline types). The term “polymorph” refers to a particular crystalline form of a chemical compound that can crystallize in different crystalline forms, these forms having different arrangements and/or conformations of the molecules in the crystal lattice. Although polymorphs can have the same chemical composition, they can also differ in composition due the presence or absence of co-crystallized water or other molecules, which can be weakly or strongly bound in the lattice. Polymorphs can differ in such chemical, physical and biological properties as crystal shape, density, hardness, color, chemical stability, melting point, hygroscopicity, suspensibility, dissolution rate and biological availability. One skilled in the art will appreciate that a polymorph of a compound of Formula 1 can exhibit beneficial effects (e.g., suitability for preparation of useful formulations, improved biological performance) relative to another polymorph or a mixture of polymorphs of the same compound of Formula 1. Preparation and isolation of a particular polymorph of a compound of Formula 1 can be achieved by methods known to those skilled in the art including, for example, crystallization using selected solvents and temperatures. For a comprehensive discussion of polymorphism see R. Hilfiker, Ed., Polymorphism in the Pharmaceutical Industry, Wiley-VCH, Weinheim, 2006.

One skilled in the art will appreciate that not all nitrogen-containing heterocycles can form N-oxides since the nitrogen requires an available lone pair for oxidation to the oxide; one skilled in the art will recognize those nitrogen-containing heterocycles which can form N-oxides. One skilled in the art will also recognize that tertiary amines can form N-oxides. Synthetic methods for the preparation of N-oxides of heterocycles and tertiary amines are very well known by one skilled in the art including the oxidation of heterocycles and tertiary amines with peroxy acids such as peracetic and m-chloroperbenzoic acid (MCPBA), hydrogen peroxide, alkyl hydroperoxides such as t-butyl hydroperoxide, sodium perborate, and dioxiranes such as dimethyldioxirane. These methods for the preparation of N-oxides have been extensively described and reviewed in the literature, see for example: T. L. Gilchrist in Comprehensive Organic Synthesis, vol. 7, pp 748-750, S. V. Ley, Ed., Pergamon Press; M. Tisler and B. Stanovnik in Comprehensive Heterocyclic Chemistry, vol. 3, pp 18-20, A. J. Boulton and A. McKillop, Eds., Pergamon Press; M. R. Grimmett and B. R. T. Keene in Advances in Heterocyclic Chemistry, vol. 43, pp 149-161, A. R. Katritzky, Ed., Academic Press; M. Tisler and B. Stanovnik in Advances in Heterocyclic Chemistry, vol. 9, pp 285-291, A. R. Katritzky and A. J. Boulton, Eds., Academic Press; and G. W. H. Cheeseman and E. S. G. Werstiuk in Advances in Heterocyclic Chemistry, vol. 22, pp 390-392, A. R. Katritzky and A. J. Boulton, Eds., Academic Press.

One skilled in the art recognizes that because in the environment and under physiological conditions salts of chemical compounds are in equilibrium with their corresponding nonsalt forms, salts share the biological utility of the nonsalt forms. Thus a wide variety of salts of a compound of Formula 1 are useful for control of undesired vegetation (i.e. are agriculturally suitable). The salts of a compound of Formula 1 include acid-addition salts with inorganic or organic acids such as hydrobromic, hydrochloric, nitric, phosphoric, sulfuric, acetic, butyric, fumaric, lactic, maleic, malonic, oxalic, propionic, salicylic, tartaric, 4-toluenesulfonic or valeric acids. Salts may also include those formed with organic or inorganic bases such as pyridine, triethylamine or ammonia, or amides, hydrides, hydroxides or carbonates of sodium, potassium, lithium, calcium, magnesium or barium. Accordingly, the present invention comprises compounds selected from Formula 1, N-oxides and agriculturally suitable salts thereof.

Embodiments of the present invention as described in the Summary of the Invention include (where Formula 1 as used in the following Embodiments includes N-oxides and salts thereof):

-   -   Embodiment 1. A compound of Formula 1 wherein A is C₂-C₈ alkyl,         C₂-C₆ alkenyl, C₂-C₆ alkynyl, C₂-C₈ haloalkyl, C₂-C₆         haloalkenyl, C₂-C₆ haloalkynyl, C₃-C₆ cycloalkyl, C₃-C₆         halocycloalkyl, C₄-C₈ alkylcycloalkyl, C₄-C₈ cycloalkylalkyl,         C₂-C₆ alkoxyalkyl, C₂-C₆ haloalkoxyalkyl, C₂-C₆ alkoxyhaloalkyl,         C₄-C₈ cycloalkoxyalkyl, C₂-C₆ cyanoalkyl, C₃-C₇         cyanoalkoxyalkyl, C₂-C₆ alkylthioalkyl, C₂-C₆         haloalkylthioalkyl, C₃-C₈ cycloalkylthioalkyl, C₂-C₆         alkylsulfonylalkyl or C₂-C₆ haloalkylsulfonylalkyl.     -   Embodiment 2. A compound of Embodiment 1 wherein A is C₂-C₈         alkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl, C₂-C₈ haloalkyl, C₂-C₆         haloalkenyl, C₂-C₆ haloalkynyl, C₃-C₆ cycloalkyl, C₃-C₆         halocycloalkyl, C₄-C₈ alkylcycloalkyl, C₄-C₈ cycloalkylalkyl,         C₂-C₆ alkoxyalkyl, C₂-C₆ haloalkoxyalkyl or C₂-C₆         alkoxyhaloalkyl.     -   Embodiment 3. A compound of Embodiment 2 wherein A is C₂-C₈         alkyl, C₂-C₈ haloalkyl, C₂-C₆ haloalkenyl, C₂-C₆ alkoxyalkyl,         C₂-C₆ haloalkoxyalkyl or C₂-C₆ alkoxyhaloalkyl.     -   Embodiment 4. A compound of Formula 1 or any one of Embodiments         1 through 3 either alone or in combination, wherein R¹ is         halogen, C₁-C₄ alkyl or C₁-C₄ haloalkyl.     -   Embodiment 5. A compound of Embodiment 4 wherein R¹ is halogen         or C₁-C₄ alkyl.     -   Embodiment 6. A compound of Embodiment 5 wherein R¹ is halogen         or CH₃.     -   Embodiment 7. A compound of Embodiment 6 wherein R¹ is halogen.     -   Embodiment 8. A compound of Embodiment 7 wherein R¹ is F, Cl or         Br.     -   Embodiment 9. A compound of Formula 1 or any one of Embodiments         1 through 8 either alone or in combination, wherein R² is         halogen, cyano, CHO, C₁-C₄ alkyl, C₂-C₄ alkenyl, C₂-C₄ alkynyl,         C₁-C₄ haloalkyl, C₂-C₄ haloalkenyl, C₂-C₄ haloalkynyl, C₃-C₆         cycloalkyl, C₃-C₆ halocycloalkyl, C₂-C₆ alkylcarbonyl, C₂-C₆         haloalkylcarbonyl, C₂-C₆ alkoxycarbonyl, C₁-C₄ alkoxy, C₁-C₄         haloalkoxy, C₂-C₆ alkoxyalkyl, C₂-C₆ haloalkoxyalkyl, C₂-C₆         cyanoalkyl or SO_(n)R⁴.     -   Embodiment 10. A compound of Embodiment 9 wherein R² is halogen,         cyano, C₁-C₄ alkyl or C₁-C₄ haloalkyl.     -   Embodiment 11. A compound of Embodiment 10 wherein R² is halogen         or cyano.     -   Embodiment 12. A compound of Embodiment 11 wherein R² is cyano.     -   Embodiment 13. A compound of Embodiment 11 wherein R² is         halogen.     -   Embodiment 14. A compound of Formula 1 or any one of Embodiments         1 through 13 either alone or in combination, wherein R³ is H.     -   Embodiment 15. A compound of Formula 1 wherein A is C₃-C₆         haloalkyl.     -   Embodiment 16. A compound of Formula 1 wherein A is C₄-C₆         haloalkyl.     -   Embodiment 17. A compound of Formula 1 wherein A is C₄-C₅         haloalkyl.     -   Embodiment 18. A compound of Formula 1 wherein A is         CH₂CH₂CH₂CF₃.     -   Embodiment 19. A compound of Formula 1 wherein A is         CH₂CH₂CF₂CF₃.     -   Embodiment 20. A compound of Formula 1 wherein A is CH₂CH₂CF₃.     -   Embodiment 21. A compound of Formula 1 wherein A is CH₂CF₃.     -   Embodiment 22. A compound of Formula 1 wherein A is C₄-C₆         haloalkenyl.     -   Embodiment 23. A compound of Formula 1 wherein A is other than         C₂-C₆ alkylcarbonyl.     -   Embodiment 24. A compound of Formula 1 wherein A is other than         C₂-C₆ haloalkylcarbonyl.     -   Embodiment 25. A compound of Formula 1 wherein A is other than         C₂-C₆ alkylcarbonylalkyl or C₂-C₆ haloalkylcarbonylalkyl.     -   Embodiment 26. A compound of Formula 1 wherein R¹ is Cl.     -   Embodiment 27. A compound of Formula 1 wherein R² is F, Cl, Br         or I.     -   Embodiment 28. A compound of Formula 1 wherein R² is Cl, Br or         I.     -   Embodiment 29. A compound of Formula 1 wherein R² is F, Cl, Br,         I, cyano, CH₃ or CF₃.     -   Embodiment 30. A compound of Formula 1 wherein G is a 5- to         6-membered nonaromatic heterocyclic ring containing ring members         selected from carbon, up to 4 heteroatoms selected from up to         2O, up to 2 S and up to 4 N, and up to 3 ring members selected         from C(═O), C(═S) and S(═O)_(a)(═NR⁶)_(b) and substituted with         up to 3 substituents independently selected from halogen, cyano,         C₁-C₄ alkyl, C₁-C₄ haloalkyl, C₁-C₄ alkoxy or C₁-C₄ haloalkoxy.     -   Embodiment 31. A compound of Formula 1 wherein A is other than         G.     -   Embodiment 32. A compound of Formula 1 wherein A is other than         C₁-C₄ alkyl substituted with Q.     -   Embodiment 33. A compound of Formula 1 wherein each R⁴ is         independently C₁-C₃ alkyl or C₁-C₃ haloalkyl.     -   Embodiment 34. A compound of Embodiment 33wherein R⁴ is CH₃,         CH₂CH₃, or CH₂CF₃.     -   Embodiment 35. A compound of Embodiment 34wherein R⁴ is CH₃ or         CH₂CH₃.

Embodiments of this invention, including Embodiments 1-35 above as well as any other embodiments described herein, can be combined in any manner, and the descriptions of variables in the embodiments pertain not only to the compounds of Formula 1 but also to the starting compounds and intermediate compounds useful for preparing the compounds of Formula 1. In addition, embodiments of this invention, including Embodiments 1-35 above as well as any other embodiments described herein, and any combination thereof, pertain to the compositions and methods of the present invention.

Combinations of Embodiments 1-35 are illustrated by:

-   Embodiment A. A compound of Formula 1 wherein     -   A is C₂-C₈ alkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl, C₂-C₆ haloalkyl,         C₂-C₆ haloalkenyl, C₂-C₆ haloalkynyl, C₃-C₆ cycloalkyl, C₃-C₆         halocycloalkyl, C₄-C₈ alkylcycloalkyl, C₄-C₈ cycloalkylalkyl,         C₂-C₆ alkoxyalkyl, C₂-C₆ haloalkoxyalkyl, C₂-C₆ alkoxyhaloalkyl,         C₄-C₈ cycloalkoxyalkyl, C₂-C₆ cyanoalkyl, C₃-C₇         cyanoalkoxyalkyl, C₂-C₆ alkylthioalkyl, C₂-C₆         haloalkylthioalkyl, C₃-C₈ cycloalkylthioalkyl, C₂-C₆         alkylsulfonylalkyl or C₂-C₆ haloalkylsulfonylalkyl;     -   R¹ is halogen, C₁-C₄ alkyl or C₁-C₄ haloalkyl;     -   R² is halogen, cyano, CHO, C₁-C₄ alkyl, C₂-C₄ alkenyl, C₂-C₄         alkynyl, C₁-C₄ haloalkyl, C₂-C₄ haloalkenyl, C₂-C₄ haloalkynyl,         C₃-C₆ cycloalkyl, C₃-C₆ halocycloalkyl, C₂-C₆ alkylcarbonyl,         C₂-C₆ haloalkylcarbonyl, C₂-C₆ alkoxycarbonyl, C₁-C₄ alkoxy,         C₁-C₄ haloalkoxy, C₂-C₆ alkoxyalkyl, C₂-C₆ haloalkoxyalkyl,         C₂-C₆ cyanoalkyl or SO_(n)R⁴; and     -   R³ is H. -   Embodiment B. A compound of Embodiment A wherein     -   A is C₂-C₈ alkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl, C₂-C₈ haloalkyl,         C₂-C₆ haloalkenyl, C₂-C₆ haloalkynyl, C₃-C₆ cycloalkyl, C₃-C₆         halocycloalkyl, C₄-C₈ alkylcycloalkyl, C₄-C₈ cycloalkylalkyl,         C₂-C₆ alkoxyalkyl, C₂-C₆ haloalkoxyalkyl or C₂-C₆         alkoxyhaloalkyl;     -   R¹ is halogen or C₁-C₄ alkyl; and     -   R² is halogen, cyano, C₁-C₄ alkyl or C₁-C₄ haloalkyl. -   Embodiment C. A compound of Embodiment B wherein     -   A is C₂-C₈ alkyl, C₂-C₈ haloalkyl, C₂-C₆ haloalkenyl, C₂-C₆         alkoxyalkyl, C₂-C₆ haloalkoxyalkyl or C₂-C₆ alkoxyhaloalkyl;     -   R¹ is halogen; and     -   R² is halogen or cyano.

Specific embodiments include compounds of Formula 1 selected from the group consisting of:

-   2-[3-bromo-2-(butoxy)phenoxy]-5-chloropyrimidine (Compound 13), -   3-[(5-chloro-2-pyrimidinyl)oxy]-2-[[(2E)-4,4,4-trifluoro-2-buten-1-yl]oxy]benzonitrile     (Compound 8), -   2-[3-bromo-2-(2,2,3,3-tetrafluoropropoxy)phenoxy]-5-chloropyrimidine     (Compound 18), -   3-[(5-chloro-2-pyrimidinyl)oxy]-2-(2,2,3,3,3-pentafluoropropoxy)benzonitrile     (Compound 10), -   2-butoxy-3-[(5-chloro-2-pyrimidinyl)oxy]benzonitrile (Compound 35), -   3-[(5-chloro-2-pyrimidinyl)oxy]-2-(3,3,3-trifluoropropoxy)benzonitrile     (Compound 23), -   3-[(5-fluoro-2-pyrimidinyl)oxy]-2-(4,4,4-trifluorobutoxy)benzonitrile     (Compound 4) and -   3-[(5-chloro-2-pyrimidinyl)oxy]-2-(4,4,4-trifluorobutoxy)benzonitrile     (Compound 5).

This invention also relates to a method for controlling undesired vegetation comprising applying to the locus of the vegetation herbicidally effective amounts of the compounds of the invention (e.g., as a composition described herein). Of note as embodiments relating to methods of use are those involving the compounds of embodiments described above. Compounds of the invention are particularly useful for selective control of weeds in crops such as wheat, barley, maize, soybean, sunflower, cotton, oilseed rape and rice, and specialty crops such as sugarcane, citrus, fruit and nut crops.

Also noteworthy as embodiments are herbicidal compositions of the present invention comprising the compounds of embodiments described above.

This invention also includes a herbicidal mixture comprising (a) a compound selected from Formula 1, N-oxides, and salts thereof, and (b) at least one additional active ingredient selected from (b1) photosystem II inhibitors, (b2) acetohydroxy acid synthase (AHAS) inhibitors, (b3) acetyl-CoA carboxylase (ACCase) inhibitors, (b4) auxin mimics, (b5) 5-enol-pyruvylshikimate-3-phosphate (EPSP) synthase inhibitors, (b6) photosystem I electron diverters, (b7) protoporphyrinogen oxidase (PPO) inhibitors, (b8) glutamine synthetase (GS) inhibitors, (b9) very long chain fatty acid (VLCFA) elongase inhibitors, (b10) auxin transport inhibitors, (b11) phytoene desaturase (PDS) inhibitors, (b12) 4-hydroxyphenyl-pyruvate dioxygenase (HPPD) inhibitors, (b13) homogentisate solenesyltransererase (HST) inhibitors, (b14) cellulose biosynthesis inhibitors, (b15) other herbicides including mitotic disruptors, organic arsenicals, asulam, bromobutide, cinmethylin, cumyluron, dazomet, difenzoquat, dymron, etobenzanid, flurenol, fosamine, fosamine-ammonium, hydantocidin, metam, methyldymron, oleic acid, oxaziclomefone, pelargonic acid and pyributicarb, and (b16) herbicide safeners; and salts of compounds of (b1) through (b16).

“Photosystem II inhibitors” (b1) are chemical compounds that bind to the D-1 protein at the Q_(B)-binding niche and thus block electron transport from Q_(A) to Q_(B) in the chloroplast thylakoid membranes. The electrons blocked from passing through photosystem II are transferred through a series of reactions to form toxic compounds that disrupt cell membranes and cause chloroplast swelling, membrane leakage, and ultimately cellular destruction. The Q_(B)-binding niche has three different binding sites: binding site A binds the triazines such as atrazine, triazinones such as hexazinone, and uracils such as bromacil, binding site B binds the phenylureas such as diuron, and binding site C binds benzothiadiazoles such as bentazon, nitriles such as bromoxynil and phenyl-pyridazines such as pyridate. Examples of photosystem II inhibitors include ametryn, amicarbazone, atrazine, bentazon, bromacil, bromofenoxim, bromoxynil, chlorbromuron, chloridazon, chlorotoluron, chloroxuron, cumyluron, cyanazine, daimuron, desmedipham, desmetryn, dimefuron, dimethametryn, diuron, ethidimuron, fenuron, fluometuron, hexazinone, ioxynil, isoproturon, isouron, lenacil, linuron, metamitron, methabenzthiazuron, metobromuron, metoxuron, metribuzin, monolinuron, neburon, pentanochlor, phenmedipham, prometon, prometryn, propanil, propazine, pyridafol, pyridate, siduron, simazine, simetryn, tebuthiuron, terbacil, terbumeton, terbuthylazine, terbutryn and trietazine.

“AHAS inhibitors” (b2) are chemical compounds that inhibit acetohydroxy acid synthase (AHAS), also known as acetolactate synthase (ALS), and thus kill plants by inhibiting the production of the branched-chain aliphatic amino acids such as valine, leucine and isoleucine, which are required for protein synthesis and cell growth. Examples of AHAS inhibitors include amidosulfuron, azimsulfuron, bensulfuron-methyl, bispyribac-sodium, cloransulam-methyl, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, cyclosulfamuron, diclosulam, ethametsulfuron-methyl, ethoxysulfuron, flazasulfuron, florasulam, flucarbazone-sodium, flumetsulam, flupyrsulfuron-methyl, flupyrsulfuron-sodium, foramsulfuron, halosulfuron-methyl, imazamethabenz-methyl, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, imazosulfuron, iodosulfuron-methyl (including sodium salt), iofensulfuron (2-iodo-N-[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)amino]carbonyl]benzenesulfonamide), mesosulfuron-methyl, metazosulfuron (3-chloro-4-(5,6-dihydro-5-methyl-1,4,2-dioxazin-3-yl)-N-[[(4,6-dimethoxy-2-pyrimidinyl)amino]carbonyl]-1-methyl-1H-pyrazole-5-sulfonamide), metosulam, metsulfuron-methyl, nicosulfuron, oxasulfuron, penoxsulam, primisulfuron-methyl, propoxycarbazone-sodium, propyrisulfuron (2-chloro-N-[[(4,6-dimethoxy-2-pyrimidinyl)amino]carbonyl]-6-propylimidazo[1,2-b]pyridazine-3-sulfonamide), prosulfuron, pyrazosulfuron-ethyl, pyribenzoxim, pyriftalid, pyriminobac-methyl, pyrithiobac-sodium, rimsulfuron, sulfometuron-methyl, sulfosulfuron, thiencarbazone, thifensulfuron-methyl, triafamone (N-[2-[(4,6-dimethoxy-1,3,5-triazin-2-yl)carbonyl]-6-fluorophenyl]-1,1-difluoro-N-methylmethanesulfonamide), triasulfuron, tribenuron-methyl, trifloxysulfuron (including sodium salt), triflusulfuron-methyl and tritosulfuron.

“ACCase inhibitors” (b3) are chemical compounds that inhibit the acetyl-CoA carboxylase enzyme, which is responsible for catalyzing an early step in lipid and fatty acid synthesis in plants. Lipids are essential components of cell membranes, and without them, new cells cannot be produced. The inhibition of acetyl CoA carboxylase and the subsequent lack of lipid production leads to losses in cell membrane integrity, especially in regions of active growth such as meristems. Eventually shoot and rhizome growth ceases, and shoot meristems and rhizome buds begin to die back. Examples of ACCase inhibitors include alloxydim, butroxydim, clethodim, clodinafop, cycloxydim, cyhalofop, diclofop, fenoxaprop, fluazifop, haloxyfop, pinoxaden, profoxydim, propaquizafop, quizalofop, sethoxydim, tepraloxydim and tralkoxydim, including resolved forms such as fenoxaprop-P, fluazifop-P, haloxyfop-P and quizalofop-P and ester forms such as clodinafop-propargyl, cyhalofop-butyl, diclofop-methyl and fenoxaprop-P-ethyl.

Auxin is a plant hormone that regulates growth in many plant tissues. “Auxin mimics” (b4) are chemical compounds mimicking the plant growth hormone auxin, thus causing uncontrolled and disorganized growth leading to plant death in susceptible species. Examples of auxin mimics include aminocyclopyrachlor (6-amino-5-chloro-2-cyclopropyl-4-pyrimidinecarboxylic acid) and its methyl and ethyl esters and its sodium and potassium salts, aminopyralid, benazolin-ethyl, chloramben, clacyfos, clomeprop, clopyralid, dicamba, 2,4-D, 2,4-DB, dichlorprop, fluroxypyr, halauxifen (4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)-2-pyridinecarboxylic acid), halauxifen-methyl (methyl 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)-2-pyridinecarboxylate), MCPA, MCPB, mecoprop, picloram, quinclorac, quinmerac, 2,3,6-TBA, triclopyr, and methyl 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)-5-fluoro-2-pyridinecarboxylate.

“EPSP synthase inhibitors” (b5) are chemical compounds that inhibit the enzyme, 5-enol-pyruvylshikimate-3-phosphate synthase, which is involved in the synthesis of aromatic amino acids such as tyrosine, tryptophan and phenylalanine. EPSP inhibitor herbicides are readily absorbed through plant foliage and translocated in the phloem to the growing points. Glyphosate is a relatively nonselective postemergence herbicide that belongs to this group. Glyphosate includes esters and salts such as ammonium, isopropylammonium, potassium, sodium (including sesquisodium) and trimesium (alternatively named sulfosate).

“Photosystem I electron diverters” (b6) are chemical compounds that accept electrons from Photosystem I, and after several cycles, generate hydroxyl radicals. These radicals are extremely reactive and readily destroy unsaturated lipids, including membrane fatty acids and chlorophyll. This destroys cell membrane integrity, so that cells and organelles “leak”, leading to rapid leaf wilting and desiccation, and eventually to plant death. Examples of this second type of photosynthesis inhibitor include diquat and paraquat.

“PPO inhibitors” (b7) are chemical compounds that inhibit the enzyme protoporphyrinogen oxidase, quickly resulting in formation of highly reactive compounds in plants that rupture cell membranes, causing cell fluids to leak out. Examples of PPO inhibitors include acifluorfen-sodium, azafenidin, benzfendizone, bifenox, butafenacil, carfentrazone, carfentrazone-ethyl, chlomethoxyfen, cinidon-ethyl, fluazolate, flufenpyr-ethyl, flumiclorac-pentyl, flumioxazin, fluoroglycofen-ethyl, fluthiacet-methyl, fomesafen, halosafen, lactofen, oxadiargyl, oxadiazon, oxyfluorfen, pentoxazone, profluazol, pyraclonil, pyraflufen-ethyl, saflufenacil, sulfentrazone, thidiazimin, trifludimoxazin (dihydro-1,5-dimehyl-6-thioxo-3-[2,2,7-trifluoro-3,4-dihydro-3-oxo-4-(2-propyn-1-yl)-2H-1,4-benzoxazin-6-yl]-1,3,5-triazine-2,4(1H,3H)-dione) and tiafenacil (methyl N-[2-[[2-chloro-5-[3,6-dihydro-3-methyl-2,6-dioxo-4-(trifluoromethyl)-1(2H)-pyrimidinyl]-4-fluorophenyl]thio]-1-oxopropyl]-β-alaninate).

“GS inhibitors” (b8) are chemical compounds that inhibit the activity of the glutamine synthetase enzyme, which plants use to convert ammonia into glutamine Consequently, ammonia accumulates and glutamine levels decrease. Plant damage probably occurs due to the combined effects of ammonia toxicity and deficiency of amino acids required for other metabolic processes. The GS inhibitors include glufosinate and its esters and salts such as glufosinate-ammonium and other phosphinothricin derivatives, glufosinate-P ((2S)-2-amino-4-(hydroxymethylphosphinyl)butanoic acid) and bilanaphos.

“VLCFA elongase inhibitors” (b9) are herbicides having a wide variety of chemical structures, which inhibit the elongase. Elongase is one of the enzymes located in or near chloroplasts which are involved in biosynthesis of VLCFAs. In plants, very-long-chain fatty acids are the main constituents of hydrophobic polymers that prevent desiccation at the leaf surface and provide stability to pollen grains. Such herbicides include acetochlor, alachlor, anilofos, butachlor, cafenstrole, dimethachlor, dimethenamid, diphenamid, fenoxasulfone (3-[[(2,5-dichloro-4-ethoxyphenyl)methyl]sulfonyl]-4,5-dihydro-5,5-dimethylisoxazole), fentrazamide, flufenacet, indanofan, mefenacet, metazachlor, metolachlor, naproanilide, napropamide, napropamide-M ((2R)-N,N-diethyl-2-(1-naphthalenyloxy)propanamide), pethoxamid, piperophos, pretilachlor, propachlor, propisochlor, pyroxasulfone, and thenylchlor, including resolved forms such as S-metolachlor and chloroacetamides and oxyacetamides.

“Auxin transport inhibitors” (b10) are chemical substances that inhibit auxin transport in plants, such as by binding with an auxin-carrier protein. Examples of auxin transport inhibitors include diflufenzopyr, naptalam (also known as N-(1-naphthyl)phthalamic acid and 2-[(1-naphthalenylamino)carbonyl]benzoic acid).

“PDS inhibitors” (b11) are chemical compounds that inhibit carotenoid biosynthesis pathway at the phytoene desaturase step. Examples of PDS inhibitors include beflubutamid, diflufenican, fluridone, flurochloridone, flurtamone norflurzon and picolinafen.

“HPPD inhibitors” (b12) are chemical substances that inhibit the biosynthesis of synthesis of 4-hydroxyphenyl-pyruvate dioxygenase. Examples of HPPD inhibitors include benzobicyclon, benzofenap, bicyclopyrone (4-hydroxy-3-[[2-[(2-methoxyethoxy)methyl]-6-(trifluoromethyl)-3-pyridinyl]carbonyl]bicyclo[3.2.1]oct-3-en-2-one), fenquinotrione (2-[[8-chloro-3,4-dihydro-4-(4-methoxyphenyl)-3-oxo-2-quinoxalinyl]carbonyl]-1,3-cyclohexanedione), isoxachlortole, isoxaflutole, mesotrione, pyrasulfotole, pyrazolynate, pyrazoxyfen, sulcotrione, tefuryltrione, tembotrione, tolpyralate (1-[[1-ethyl-4-[3-(2-methoxyethoxy)-2-methyl-4-(methylsulfonyl)benzoyl]-1H-pyrazol-5-yl]oxy]ethyl methyl carbonate), topramezone, 5-chloro-3-[(2-hydroxy-6-oxo-1-cyclohexen-1-yl)carbonyl]-1-(4-methoxyphenyl)-2(1H)-quinoxalinone, 4-(2,6-diethyl-4-methylphenyl)-5-hydroxy-2,6-dimethyl-3(2H)-pyridazinone, 4-(4-fluorophenyl)-6-[(2-hydroxy-6-oxo-1-cyclohexen-1-yl)carbonyl]-2-methyl-1,2,4-triazine-3,5(2H,4H)-dione, 5-[(2-hydroxy-6-oxo-1-cyclohexen-1-yl)carbonyl]-2-(3-methoxyphenyl)-3-(3-methoxypropyl)-4(3H)-pyrimidinone, 2-methyl-N-(4-methyl-1,2,5-oxadiazol-3-yl)-3-(methylsulfinyl)-4-(trifluoromethyl)benzamide and 2-methyl-3-(methylsulfonyl)-N-(1-methyl-1H-tetrazol-5-yl)-4-(trifluoromethyl)benzamide.

“HST inhibitors” (b13) disrupt a plant's ability to convert homogentisate to 2-methyl-6-solanyl-1,4-benzoquinone, thereby disrupting carotenoid biosynthesis. Examples of HST inhibitors include haloxydine, cyclopyrimorate (6-chloro-3-(2-cyclopropyl-6-methylphenoxy)-4-pyridazinyl 4-morpholinecarboxylate), pyriclor, 3-(2-chloro-3,6-difluorophenyl)-4-hydroxy-1-methyl-1,5-naphthyridin-2(1H)-one, 7-(3,5-dichloro-4-pyridinyl)-5-(2,2-difluoroethyl)-8-hydroxypyrido[2,3-b]pyrazin-6(5H)-one and 4-(2,6-diethyl-4-methylphenyl)-5-hydroxy-2,6-dimethyl-3 (2H)-pyridazinone.

HST inhibitors also include compounds of Formulae A and B.

-   -   wherein R^(d1) is H, Cl or CF₃; R^(d2) is H, Cl or Br; R^(d3) is         H or Cl; R^(d4) is H, Cl or CF₃; R^(d5) is CH₃, CH₂CH₃ or         CH₂CHF₂; and R^(d6) is OH, or —OC(═O)-i-Pr; and R^(e1) is H, F,         Cl, CH₃ or CH₂CH₃; R^(e2) H or CF₃; R^(e3) H, CH₃ or CH₂CH₃;         R^(e4) is H, F or Br; R^(e5) Cl, CH₃, CF₃, OCF₃ or CH₂CH₃;         R^(e6) is H, CH₃, CH₂CHF₂ or C≡CH; R^(e7) is OH, —OC(═O)Et,         —OC(═O)-i-Pr or —OC(═O)-t-Bu; and A^(e8) is N or CH.

“Cellulose biosynthesis inhibitors” (b14) inhibit the biosynthesis of cellulose in certain plants. They are most effective when applied preemergence or early postemergence on young or rapidly growing plants. Examples of cellulose biosynthesis inhibitors include chlorthiamid, dichlobenil, flupoxam, indaziflam (N²-[(1R,2S)-2,3-dihydro-2,6-dimethyl-1H-inden-1-yl]-6-(1-fluoroethyl)-1,3,5-triazine-2,4-diamine), isoxaben and triaziflam.

“Other herbicides” (b15) include herbicides that act through a variety of different modes of action such as mitotic disruptors (e.g., flamprop-M-methyl and flamprop-M-isopropyl), organic arsenicals (e.g., DSMA, and MSMA), 7,8-dihydropteroate synthase inhibitors, chloroplast isoprenoid synthesis inhibitors and cell-wall biosynthesis inhibitors. Other herbicides include those herbicides having unknown modes of action or do not fall into a specific category listed in (b1) through (b14) or act through a combination of modes of action listed above. Examples of other herbicides include aclonifen, asulam, amitrole, bromobutide, cinmethylin, clomazone, cumyluron, daimuron, difenzoquat, etobenzanid, fluometuron, flurenol, fosamine, fosamine-ammonium, dazomet, dymron, ipfencarbazone (1-(2,4-dichlorophenyl)-N-(2,4-difluorophenyl)-1,5-dihydro-N-(1-methylethyl)-5-oxo-4H-1,2,4-triazole-4-carboxamide), metam, methyldymron, oleic acid, oxaziclomefone, pelargonic acid, pyributicarb and 5-[[(2,6-difluorophenyl)methoxy]methyl]-4,5-dihydro-5-methyl-3-(3-methyl-2-thienyl)isoxazole.

“Herbicide safeners” (b16) are substances added to a herbicide formulation to eliminate or reduce phytotoxic effects of the herbicide to certain crops. These compounds protect crops from injury by herbicides but typically do not prevent the herbicide from controlling undesired vegetation. Examples of herbicide safeners include but are not limited to benoxacor, cloquintocet-mexyl, cumyluron, cyometrinil, cyprosulfamide, daimuron, dichlormid, dicyclonon, dietholate, dimepiperate, fenchlorazole-ethyl, fenclorim, flurazole, fluxofenim, furilazole, isoxadifen-ethyl, mefenpyr-diethyl, mephenate, methoxyphenone, naphthalic anhydride, oxabetrinil, N-(aminocarbonyl)-2-methylbenzenesulfonamide and N-(aminocarbonyl)-2-fluorobenzenesulfonamide, 1-bromo-4-[(chloromethyl)sulfonyl]benzene, 2-(dichloromethyl)-2-methyl-1,3-dioxolane (MG 191), 4-(dichloroacetyl)-1-oxa-4-azospiro[4.5]decane (MON 4660), 2,2-dichloro-1-(2,2,5-trimethyl-3-oxazolidinyl)-ethanone and 2-methoxy-N-[[4-[[(methylamino)carbonyl]amino]phenyl]sulfonyl]-benzamide.

An embodiment of the present invention is a herbicidal mixture comprising (a) a compound of Formula 1, and (b) at least one additional active ingredient selected from (b1) photosystem II inhibitors, (b2) acetohydroxy acid synthase (AHAS) inhibitors, (b4) auxin mimics, (b5) 5-enol-pyruvylshikimate-3-phosphate (EPSP) synthase inhibitors, (b7) protoporphyrinogen oxidase (PPO) inhibitors, (b9) very long chain fatty acid (VLCFA) elongase inhibitors and (b12) 4-hydroxyphenyl-pyruvate dioxygenase (HPPD) inhibitors.

The compounds of Formula 1 can be prepared by general methods known in the art of synthetic organic chemistry. One or more of the following methods and variations as described in Schemes 1-7 can be used to prepare the compounds of Formula 1. The definitions of A, R¹ and R² in the compounds of Formulae 1-12 below are as defined above in the Summary of the Invention unless otherwise noted.

As shown in Scheme 1, a compound of Formula 1 (wherein R³ is H) can be prepared by nucleophilic substitution by heating a phenolic intermediate of Formula 2 in a suitable solvent, such as acetonitrile, tetrahydrofuran or N,N-dimethylformamide, in the presence of a base, such as potassium or cesium carbonate, with a compound of Formula 3 (where LG is a nucleophilic reaction leaving group, i.e. nucleofuge, such as halogen or S(O)₂CH₃). The reaction is typically conducted at temperatures ranging from 50 to 110° C.

As shown in Scheme 2, compounds of Formula 1 can be prepared by nucleophilic displacement on an alkylating agent with a phenol of Formula 4 in the presence of a suitable acid acceptor. Suitable acid acceptors include, but are not limited to, sodium hydride, potassium t-butoxide, sodium carbonate, potassium carbonate, cesium carbonate, sodium hydroxide, and potassium hydroxide. Suitable solvents include acetonitrile, N,N-dimethylacetamide or N,N-dimethylformamide The reaction is typically conducted at temperatures ranging from 0 to 110° C.

As shown in Scheme 3, compounds of Formula 1 may also be prepared by the Mitsunobu reaction of alcohols of Formula 6 with phenols of Formula 4. This reaction is well known in the art and requires the presence of a diazodicarboxylate and a phosphine. Diethyl (DEAD) and diisopropylazodicarboxylate (DIAD) are particularly useful reagents in this process. Triphenylphosphine is a particularly useful phosphine. The reaction can be performed in various solvents with tetrahydrofuran being particularly useful. The reaction may be carried out at temperatures from 0 to 100° C. A useful review of this reaction is found in Hughes, Organic Reactions 1992, 42: 335-656.

Compounds of Formula 4 can be prepared by the dealkylation reaction of compounds of Formula 7 with a dealkylation reagent as shown in Scheme 4. A suitable deprotecting agent such as BBr₃, AlCl₃, Me₃SiI and HBr in acetic acid, can be used in the presence of solvents such as toluene, dichloromethane and dichloroethane at a temperature ranging from −80 to 120° C. Other useful phenolic protecting groups suitable for use in preparing a compound of Formula 4 can be found in Greene, T. W.; Wuts, P. G. M. Protective Groups in Organic Synthesis, 4^(th) ed.; Wiley: Hoboken, N.J. 2012).

Compounds of Formula 4 may also be prepared by the reaction of compounds of Formula 8 with compounds of Formula 3 in the presence of an acid acceptor as shown in Scheme 5. The compound of Formula 4 can be prepared by nucleophilic substitution by heating a catechol intermediate of Formula 8 in a suitable solvent, such as acetone, acetonitrile, N,N-dimethylacetamide or N,N-dimethylformamide, in the presence of a base, such as potassium or cesium carbonate, with a compound of Formula 3 (where LG is a nucleophilic reaction leaving group such as halogen or S(O)₂CH₃). The reaction is typically conducted at temperatures ranging from 50 to 110° C. In cases where mixtures of regioisomeric products are formed they may be directly utilized under the conditions of Schemes 2 and 3 and the compounds of Formula 1 may be isolated in pure form by separation techniques known to those skilled in the art such as chromatography and crystallization.

Compounds of Formula 9 (wherein R² is an electron withdrawing group) can be prepared by selective methylation of compounds of Formula 8 with a methylation agent of Formula 9 in the presence of an acid acceptor as shown in Scheme 6. Suitable methylation reagents include methyl iodide, methyl bromide, dimethylsulfate, and methyl triflate. Suitable acid acceptors include, but are not limited to, sodium bicarbonate, potassium bicarbonate, sodium carbonate, potassium carbonate, cesium carbonate, sodium hydroxide, and potassium hydroxide. Suitable solvents include acetonitrile, N,N-dimethylacetamide or N,N-dimethylformamide The reaction is typically conducted at temperatures ranging from 0 to 50° C.

Compounds of Formula 8 are generally known in the art or are commercially available. They also may be prepared by the sequence outlined in Scheme 7 by ortho-lithiation of the acetonide compound of Formula 11 and subsequent reaction with an electrophile to introduce the R² substituent. Examples of electrophile reagents and the R² groups they introduce are Br₂ (R² is Br), BrCF₂CF₂Br (R² is Br), N,N-dimethylformamide (R² is CHO), N,N-dimethylacetamide (R² is COCH₃), Cl₃CCCl₃ (R² is Cl), CO₂ (R² is CO₂H), ClCO₂CH₂CH₃ (R² is CO₂CH₂CH₃) and CH₃SSCH₃ (R² is SCH₃). The acetonide of Formula 12 can be deprotected under acidic conditions by use of reagents such as hydrochloric acid or trifluoroacetic acid in solvents such as dichloromethane, ether, water, methanol, or ethanol. Conditions and reagents for this route are described in Journal of Chemical Research, Synopses, (12), 500-501; 1994.

It is recognized by one skilled in the art that various functional groups can be converted into others to provide different compounds of Formula 1. For a valuable resource that illustrates the interconversion of functional groups in a simple and straightforward fashion, see Larock, R. C., Comprehensive Organic Transformations: A Guide to Functional Group Preparations, 2nd Ed., Wiley-VCH, New York, 1999. For example, intermediates for the preparation of compounds of Formula 1 may contain aromatic nitro groups, which can be reduced to amino groups, and then be converted via reactions well known in the art such as the Sandmeyer reaction, to various halides, providing compounds of Formula 1. The above reactions can also in many cases be performed in alternate order

It is recognized that some reagents and reaction conditions described above for preparing compounds of Formula 1 may not be compatible with certain functionalities present in the intermediates. In these instances, the incorporation of protection/deprotection sequences or functional group interconversions into the synthesis will aid in obtaining the desired products. The use and choice of the protecting groups will be apparent to one skilled in chemical synthesis (see, for example, Greene, T. W.; Wuts, P. G. M. Protective Groups in Organic Synthesis, 2nd ed.; Wiley: New York, 1991). One skilled in the art will recognize that, in some cases, after the introduction of a given reagent as depicted in any individual scheme, it may be necessary to perform additional routine synthetic steps not described in detail to complete the synthesis of compounds of Formula 1. One skilled in the art will also recognize that it may be necessary to perform a combination of the steps illustrated in the above schemes in an order other than that implied by the particular presented to prepare the compounds of Formula 1.

One skilled in the art will also recognize that compounds of Formula 1 and the intermediates described herein can be subjected to various electrophilic, nucleophilic, radical, organometallic, oxidation, and reduction reactions to add substituents or modify existing substituents.

Without further elaboration, it is believed that one skilled in the art using the preceding description can utilize the present invention to its fullest extent. The following non-limiting Examples are illustrative of the invention. Steps in the following Examples illustrate a procedure for each step in an overall synthetic transformation, and the starting material for each step may not have necessarily been prepared by a particular preparative run whose procedure is described in other Examples or Steps. Percentages are by weight except for chromatographic solvent mixtures or where otherwise indicated. Parts and percentages for chromatographic solvent mixtures are by volume unless otherwise indicated. ¹H NMR spectra are reported in ppm downfield from tetramethylsilane; “s” means singlet, “d” means doublet, “t” means triplet, “q” means quartet, “m” means multiplet, “dd” means doublet of doublets, “dt” means doublet of triplets, and “br s” means broad singlet. Mass spectra (MS) are reported as the molecular weight of the highest isotopic abundance parent ion (M+1) formed by addition of H+ (molecular weight of 1) to the molecule, or (M−1) formed by the loss of H+ (molecular weight of 1) from the molecule, observed by using liquid chromatography coupled to a mass spectrometer (LCMS) using either atmospheric pressure chemical ionization (AP+) where “amu” stands for unified atomic mass units.

EXAMPLE 1 Preparation of 2-butoxy-3-[(5-chloro-2-pyrimidinyl)oxy]benzonitrile (Compound 35) Step A: Preparation of 3-[(5-chloro-2-pyrimidinyl)oxy]-2-methoxybenzonitrile

3-Hydroxy-2-methoxybenzonitrile (730 mg, 4.9 mmol) and 2,5-dichloropyrimidine (803 mg, 5.4 mmol) were combined in acetonitrile (10 mL) under a nitrogen atmosphere. Powdered potassium carbonate (1.48 g, 10.7 mmol) was added, and the resulting mixture was heated at 80° C. for 1 hour. The reaction mixture was cooled and concentrated under reduced pressure. The residue was purified by medium pressure liquid chromatography on silica gel eluting with 0 to 20% ethyl acetate in hexanes to yield the title compound (1 g).

MS(AP⁺) 262 amu (M+1).

Step B: Preparation of 3-[(5-chloro-2-pyrimidinyl)oxy]-2-hydroxybenzonitrile

3-[(5-Chloro-2-pyrimidinyl)oxy]-2-methoxybenzonitrile (i.e. the product of Step A) (1.00 g, 3.82 mmol) was dissolved in dichloromethane (5 mL) and cooled to 0° C. Then boron tribromide (1 M in dichloromethane, 19.1 mL, 19.1 mmol) was added to the solution, and the mixture was stirred at room temperature for 3 hours. The reaction mixture was treated with saturated aqueous sodium hydrogencarbonate solution at 0° C. The aqueous phase was separated and extracted with dichloromethane. The combined organic phases were washed with saturated aqueous sodium chloride solution, dried over magnesium sulfate, filtered and concentrated under reduced pressure. The residue was used in the next step without further purification.

MS(AP⁺) 246 amu (M−1).

Step C: Preparation of 2-butoxy-3-[(5-chloro-2-pyrimidinyl)oxy]benzonitrile

To 3-[(5-chloro-2-pyrimidinyl)oxy]-2-hydroxybenzonitrile (i.e. the product of Step B) 100 mg, 0.4 mmol) and potassium carbonate (170 mg, 1.2 mmol) in acetonitrile (2 mL) was added 1-bromobutane (60 mg, 0.44 mmol). The mixture was heated at reflux for 4 hours. The reaction mixture was partitioned between water (20 mL) and ethyl acetate (20 mL). The aqueous phase was washed with ethyl acetate (2×10 mL). The combined organic phases were washed with saturated aqueous sodium chloride solution (20 mL), dried over magnesium sulfate, filtered and concentrated under reduced pressure. The crude residue was purified by medium pressure liquid chromatography on silica gel (12 g) eluted with a gradient of 0 to 30% ethyl acetate in hexanes to afford the title compound, a compound of the present invention, (90 mg).

¹H NMR (400 MHz, CDCl₃) δ8.49 (s, 2H), 7.51 (d, 1H), 7.41 (d, 1H), 7.19 t, 1H), 4.17 (t, 1H), 1.60 (m, 2H), 1.31 (m, 2H), 0.87 (t, 3H).

EXAMPLE 2 Preparation of 2[3-bromo-2-(butoxy)phenoxy]-5-chloropyrimidine (Compound 13) Step A: Preparation of 2-[3-bromo-2-(methoxy)phenoxy]-5-chloropyrimidine

3-Bromo-2-methoxyphenol (5.0 g, 24 mmol) was dissolved in 50 mL of acetonitrile and treated with potassium carbonate (8.5 g, 61 mmol) and 2,5-dichloropyrimidine (4.0 g, 27 mmol). The mixture was heated to 80° C. for 4 hours. The mixture was cooled and partitioned between water (50 mL) and ethyl acetate (50 mL). The aqueous phase was extracted with ethyl acetate (50 mL). The combined organic phases were washed with saturated aqueous sodium chloride solution (30 mL), dried over magnesium sulfate, filtered and concentrated under reduced pressure. The residue was purified by chromatography on 80 g of silica gel eluting with 10% ethyl acetate in hexanes to afford the title compound as an oil (8.3 g).

¹H NMR (400 MHz, CDCl₃) δ8.48 (s, 2H), 7.43 (d, 1H), 7.19 (d, 1H), 3.80 (s, 3H).

Step B: Preparation of 2-[3-bromo-2-(hydroxy)phenoxy]-5-chloropyrimidine

2[3-Bromo-2-(methoxy)phenoxy]-5-chloropyrimidine (i.e. the product of Step A) (4.0 g, 12 mmol) was stirred in dichloromethane (60 mL) and cooled with an ice bath. Boron tribromide (1 M in dichloromethane, 23 mL, 23 mmol) was added. The cooling bath was removed and the mixture was stirred at 23° C. for 14 hours. The mixture was poured into ice water (80 mL). The phases were separated and the aqueous phase was extracted (2×40 mL) with dichloromethane. The combined organic phases were dried over magnesium sulfate and concentrated under reduced pressure. The residue was triturated with a mixture of hexanes and diethyl ether (10 to 1, 30 mL) to give the title compound as a white solid (2.83 g).

¹H NMR (400 MHz, CDCl₃) δ8.50 (s, 2H), 7.41 (d, 1H), 7.17 (d, 1H), 6.88 (t, 1H), 5.84 (s, 1H).

Step C: Preparation of 2-[3-bromo-2-(butoxy)phenoxy]-5-chloropyrimidine

2[3-Bromo-2-(hydroxy)phenoxy]-5-chloropyrimidine (i.e. the product of Step B) (0.2 g, 0.66 mmol) was dissolved in acetonitrile (4 mL) and treated with potassium carbonate (0.28 g, 1.99 mmol) and 4-bromobutane (0.10 g, 0.73 mmol). The mixture was heated at 70° C. for 2 hours and stirred at 23° C. for 14 hours. The mixture was poured into water (15 mL) and extracted twice with ethyl acetate (10 mL). The combined organic phases were washed with saturated aqueous sodium chloride solution (10 mL), dried over magnesium sulfate, filtered and concentrated under reduced pressure. The residue was purified by chromatography on silica gel (12 g) eluting with a gradient of 0 to 30% ethyl acetate in hexanes to afford the title compound, a compound of the present invention, as an oil (140 mg).

¹H NMR (400 MHz, CDCl₃) δ8.48 (s, 2H), 7.43 (d, 1H), 7.16 (d, 1H), 7.03 (t, 1H), 3.99 (t, 2H), 1.59 (m, 2H), 1.31 (m, 2H), 0.87 (t, 3H).

EXAMPLE 3 Preparation of 2-[3-bromo-2-(2,2,3,3,4,4,4-heptafluorobutoxy)phenoxy]-5-chloropyrimidine (Compound 52) Step A: Preparation of 2-[3-bromo-2-(2,2,3,3,4,4,4-heptafluorobutoxy)phenoxy]-5-chloropyrimidine

2[3-Bromo-2-(hydroxy)phenoxy]-5-chloropyrimidine (i.e. the product obtained in Example 2, Step B) (0.1 g, 0.332 mmoles) was dissolved in 2 mL of acetonitrile under a nitrogen atmosphere. Powdered potassium carbonate (0.14 g, 0.995 mmol) was added followed by 2,2,3,3,4,4,4-heptafluoro-1-iodobutane (0.12 g, 0.365 mmoles). The resulting reaction mixture was heated at 70° C. for 4 h, then warmed to ambient temperature over 16 h. Added 2,2,3,3,4,4,4-heptafluorobutyl trifluoromethane sulfonate (0.12 g, 0.361 mmol) and heated at 50° C. for 2 hours and cooled to ambient temperature. The mixture was diluted with de-ionized water and ethyl acetate. The organic layer was decanted and the aqueous layer was extracted with ethyl acetate (2×). The combined organic layers were washed with brine, dried over magnesium sulfate and concentrated. The resulting oil was purified by silica gel column chromatography eluting with a gradient of hexanes to 25% ethyl aceatate in hexanes to isolate the title compound as an oil (45 mg). MS. (ES+)=483.3 (Br, Cl pattern).

By the procedures described herein together with methods known in the art, the following compounds of Tables 1 to 103 can be prepared. The following abbreviations are used in the Tables which follow: t means tertiary, s means secondary, n means normal, i means iso, c means cyclo, Me means methyl, Et means ethyl, Pr means propyl, Bu means butyl, i-Pr means isopropyl, Bu means butyl, c-Pr cyclopropyl, c-Bu means cyclobutyl, Ph means phenyl, OMe means methoxy, OEt means ethoxy, SMe means methylthio, SEt means ethylthio, NHMe methylamino and CN means cyano.

TABLE 1

A A n-butyl 4,4-difluoro-2-butyn-1-yl tert-butyl 5,5,5-trifluoro-1-methyl-2-pentyn- 1-yl ethyl 5,5,5-trifluoro-2-pentyn-1-yl n-hexyl 5,5,5-trifluoro-3-pentyn-1-yl isobutyl 2-cyclobutylethyl isopentyl cyclohexyl neopentyl cyclopentylmethyl methyl 4,4-difluorocyclohexan-1-yl n-pentyl 2-cyclopropylethyl n-propyl 2-methyl-3-nitro-prop-1-yl benzyl 4-nitrobut-1-yl allyl 2-nitroethyl 3-buten-1-yl 5-nitropent-1-yl 3-methyl-2-buten-1-yl 3,3-difluoro-5-methoxy-pentyl 3-methyl-3-buten-1-yl 2-(cyclopentylthio)ethyl 4-methyl-3-penten-1-yl 2-isopropoxyethyl 3-penten-1-yl 2-methoxyethyl 3-butyn-1-yl 2-(2,2,2-trifluoroethoxy)ethyl 4-methyl-2-pentyn-1-yl 2-ethoxyethyl 3-pentyn-1-yl 4-cyanobut-1-yl 2-propyn-1-yl 2-cyanoethyl 5-hexyn-1-yl 5-cyanopent-1-yl 4-pentyn-1-yl 3-cyanoprop-1-yl 3-fluoroprop-1-yl (2,2-dimethylcyclopropyl)methyl 3-chloroprop-1-yl (2,2-difluorocyclopropyl)methyl 4,4-difluorobut-1-yl 2-(2,2-difluorocyclopropyl)ethyl 2,2-difluoroethyl 2-(methylthio)ethyl 1,1,2,2-tetrafluoroethyl 2-(2,2,2-trifluoroethylthio)ethyl 3,3-difluoroprop-1-yl 2-(methylsulfinyl)ethyl 3,3,3-trifluoroprop-1-yl 2-(2,2,2-trifluoroethylsulfinyl)ethyl 3,3,4,4,4-pentafluorobut-1-yl 2-(methylsulfonyl)ethyl 2,2,3,3,3-pentafluoroprop-1-yl 2-(2,2,2-trifluoroethylsulfonyl)ethyl 3,3,4,4-tetrafluorobut-1-yl CH₂C(═O)CF₃ 2,2,3,3-tetrafluoroprop-1-yl CH₂C(═O)CH₂CH₃ 3,3,3-trichloroprop-1-yl CH₂CO₂Et 4,4,4-trifluorobut-1-yl CH₂CH₂CH₂CO₂Me 2,2,2-trifluoroethyl CH₂CO₂CH₂CF₃ 5,5,5-trifluoropent-1-yl 2-tetrahydropyranyl 4,4,5,5,5-pentafluoropent-1-yl 2-tetrahydrofuranyl 6,6,6-trifluorohex-1-yl 4-tetrahydropyranyl 4,4,4-trifluoro-2-methyl-butyl 3-oxetanyl 4-bromo-3-buten-1-yl CH₂(2-Cl—Ph) 2-chloroallyl CH₂(3-Cl—Ph) 3-chloroallyl CH₂(4-Cl—Ph) 3,3-dichloroallyl CH₂(3-CF₃—Ph) 3-chloro-3-buten-1-yl CH₂(2-CF₃—Ph) 4-chloro-3-buten-1-yl CH₂(4-CF₃—Ph) 5,5-difluoro-3-penten-1-yl CH₂(2-F—Ph) 4,4,4-trifluoro-2-buten-1-yl CH₂(3-F—Ph) 3-chloro-4,4,4-trifluoro-2-buten-1-yl CH₂(4-F—Ph) 5,5,5-trifluoro-3-methyl-2-penten-1-yl CH₂(5-chloropyridin-2-yl) 5,5,5-trifluoro-3-penten-1-yl CH₂(6-chloropyridin-2-yl) 4-bromo-3-butyn-1-yl CH₂(2-chloropyridin-5-yl) 3-butyn-1-yl CH₂(2-chloropyridin-4-yl) 4-chloro-3-butyn-1-yl CH₂(2-chloro-thiazol-5-yl) 3-chloro-2-propyn-1-yl R¹ = Cl, R² = Br and R³ = H

The present disclosure also includes Tables 2 through 103. Each Table is constructed in the same manner as Table 1 above, except that the row heading in Table 1 (i.e. “R¹=Cl, R²=Br and R³=H”) is replaced with the respective row heading shown below. For example, the first entry in Table 2 is a compound of Formula 1 wherein R¹=Cl, R²=Cl, R³=H and A is n-butyl. Tables 3 through 103 are constructed similarly.

Header Row Table R¹ R² R³ 2 Cl Cl H 3 Cl F H 4 Cl CN H 5 Cl NO₂ H 6 Cl CHO H 7 Cl C(═O)NH₂ H 8 Cl C(═S)NH₂ H 9 Cl SO₂NH₂ H 10 Cl Me H 11 Cl Et H 12 Cl vinyl H 13 Cl ethynyl H 14 Cl CF₂H H 15 Cl CH₂F H 16 Cl CF₃ H 17 Cl CH═CF₂ H 18 Cl C≡CBr H 19 Cl c-propyl H 20 Cl 2,2-di-F-c-propyl H 21 Cl CH₂(c-propyl) H 22 Cl 2-methyl-c-propyl H 23 Cl C(═O)Me H 24 Cl C(═O)CF₃ H 25 Cl CO₂Me H 26 Cl C(═O)(c-propyl) H 27 Cl OEt H 28 Cl O-allyl H 29 Cl O-c-pentyl H 30 Cl O-propargyl H 31 Cl OCF₂H H 32 Cl O-(2,2-di-F-c-propyl)CH₂ H 33 Cl O—CH₂(c-propyl) H 34 Cl OCH₂CH₂OMe H 35 Cl OCH₂CO₂Me H 36 Cl OCH₂CN H 37 Cl CONHMe H 38 Cl CONMe₂ H 39 Cl C(═NOMe)H H 40 Cl C(═NNH(Me))H H 41 Cl SMe H 42 Cl SCF₂H H 43 Cl SCF₃ H 44 Cl OCF₃ H 45 Cl I H 46 Cl 1-propyn-1-yl H 47 F I H 48 F Br H 49 F Cl H 50 F F H 51 F CN H 52 F CF₂H H 53 Br I H 54 Br Br H 55 Br Cl H 56 Br F H 57 Br CN H 58 Br CF₃ H 59 Me I H 60 Me Br H 61 Me Cl H 62 Me F H 63 Me CN H 64 Me CF₂H H 65 CF3 I H 66 CF3 Br H 67 CF3 Cl H 68 CF3 F H 69 CF3 CN H 70 CF3 CF₂H H 71 vinyl Br H 72 vinyl Cl H 73 vinyl CN H 74 ethynyl Br H 75 ethynyl Cl H 76 ethynyl CN H 77 OMe Br H 78 OMe Cl H 79 OMe CN H 80 SMe Br H 81 SMe Cl H 82 SMe CN H 83 F OCF₂H H 84 Br OCF₂H H 85 Me OCF₂H H 86 CF3 OCF₂H H 87 I OCF₂H H 88 Cl Br F 89 Cl Cl F 90 Cl F F 91 Cl CN F 92 Br Br F 93 Br Cl F 94 Br F F 95 Br CN F 96 F Br F 97 F Cl F 98 F F F 99 F CN F 100 CF₃ Br F 101 CF₃ Cl F 102 CF₃ F F 103 CF₃ CN F

A compound of this invention will generally be used as a herbicidal active ingredient in a composition, i.e. formulation, with at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents, which serves as a carrier. The formulation or composition ingredients are selected to be consistent with the physical properties of the active ingredient, mode of application and environmental factors such as soil type, moisture and temperature.

Useful formulations include both liquid and solid compositions. Liquid compositions include solutions (including emulsifiable concentrates), suspensions, emulsions (including microemulsions, oil-in -water emulsions, flowable concentrates and/or suspoemulsions) and the like, which optionally can be thickened into gels. The general types of aqueous liquid compositions are soluble concentrate, suspension concentrate, capsule suspension, concentrated emulsion, microemulsion, oil-in-water emulsion, flowable concentrate and suspo-emulsion. The general types of nonaqueous liquid compositions are emulsifiable concentrate, microemulsifiable concentrate, dispersible concentrate and oil dispersion.

The general types of solid compositions are dusts, powders, granules, pellets, prills, pastilles, tablets, filled films (including seed coatings) and the like, which can be water-dispersible (“wettable”) or water-soluble. Films and coatings formed from film-forming solutions or flowable suspensions are particularly useful for seed treatment. Active ingredient can be (micro)encapsulated and further formed into a suspension or solid formulation; alternatively the entire formulation of active ingredient can be encapsulated (or “overcoated”). Encapsulation can control or delay release of the active ingredient. An emulsifiable granule combines the advantages of both an emulsifiable concentrate formulation and a dry granular formulation. High-strength compositions are primarily used as intermediates for further formulation.

Sprayable formulations are typically extended in a suitable medium before spraying. Such liquid and solid formulations are formulated to be readily diluted in the spray medium, usually water, but occasionally another suitable medium like an aromatic or paraffinic hydrocarbon or vegetable oil. Spray volumes can range from about from about one to several thousand liters per hectare, but more typically are in the range from about ten to several hundred liters per hectare. Sprayable formulations can be tank mixed with water or another suitable medium for foliar treatment by aerial or ground application, or for application to the growing medium of the plant. Liquid and dry formulations can be metered directly into drip irrigation systems or metered into the furrow during planting.

The formulations will typically contain effective amounts of active ingredient, diluent and surfactant within the following approximate ranges which add up to 100 percent by weight.

Weight Percent Active Ingredient Diluent Surfactant Water-Dispersible and Water- 0.001-90 0-99.999 0-15 soluble Granules, Tablets and Powders Oil Dispersions, Suspensions,    1-50 40-99    0-50 Emulsions, Solutions (including Emulsifiable Concentrates) Dusts    1-25 70-99    0-5  Granules and Pellets 0.001-99 5-99.999 0-15 High Strength Compositions   90-99 0-10    0-2 

Solid diluents include, for example, clays such as bentonite, montmorillonite, attapulgite and kaolin, gypsum, cellulose, titanium dioxide, zinc oxide, starch, dextrin, sugars (e.g., lactose, sucrose), silica, talc, mica, diatomaceous earth, urea, calcium carbonate, sodium carbonate and bicarbonate, and sodium sulfate. Typical solid diluents are described in Watkins et al., Handbook of Insecticide Dust Diluents and Carriers, 2nd Ed., Dorland Books, Caldwell, N.J.

Liquid diluents include, for example, water, N,N-dimethylalkanamides (e.g., N,N-dimethylformamide), limonene, dimethyl sulfoxide, N-alkylpyrrolidones (e.g., N-methylpyrrolidinone), alkyl phosphates (e.g., triethyl phosphate), ethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, propylene carbonate, butylene carbonate, paraffins (e.g., white mineral oils, normal paraffins, isoparaffins), alkylbenzenes, alkylnaphthalenes, glycerine, glycerol triacetate, sorbitol, aromatic hydrocarbons, dearomatized aliphatics, alkylbenzenes, alkylnaphthalenes, ketones such as cyclohexanone, 2-heptanone, isophorone and 4-hydroxy-4-methyl-2-pentanone, acetates such as isoamyl acetate, hexyl acetate, heptyl acetate, octyl acetate, nonyl acetate, tridecyl acetate and isobornyl acetate, other esters such as alkylated lactate esters, dibasic esters, alkyl and aryl benzoates and γ-butyrolactone, and alcohols, which can be linear, branched, saturated or unsaturated, such as methanol, ethanol, n-propanol, isopropyl alcohol, n-butanol, isobutyl alcohol, n-hexanol, 2-ethylhexanol, n-octanol, decanol, isodecyl alcohol (e.g., isodecyl alcohol ethoxylate), isooctadecanol, cetyl alcohol, lauryl alcohol, tridecyl alcohol, oleyl alcohol, cyclohexanol, tetrahydrofurfuryl alcohol, diacetone alcohol, cresol and benzyl alcohol. Liquid diluents also include glycerol esters of saturated and unsaturated fatty acids (typically C₆-C₂₂), such as plant seed and fruit oils (e.g., oils of olive, castor, linseed, sesame, corn (maize), peanut, sunflower, grapeseed, safflower, cottonseed, soybean, rapeseed, coconut and palm kernel), animal-sourced fats (e.g., beef tallow, pork tallow, lard, cod liver oil, fish oil), and mixtures thereof. Liquid diluents also include alkylated fatty acids (e.g., methylated, ethylated, butylated) wherein the fatty acids may be obtained by hydrolysis of glycerol esters from plant and animal sources, and can be purified by distillation. Typical liquid diluents are described in Marsden, Solvents Guide, 2nd Ed., Interscience, New York, 1950.

The solid and liquid compositions of the present invention often include one or more surfactants. When added to a liquid, surfactants (also known as “surface-active agents”) generally modify, most often reduce, the surface tension of the liquid. Depending on the nature of the hydrophilic and lipophilic groups in a surfactant molecule, surfactants can be useful as wetting agents, dispersants, emulsifiers or defoaming agents.

Surfactants can be classified as nonionic, anionic or cationic. Nonionic surfactants useful for the present compositions include, but are not limited to: alcohol alkoxylates such as alcohol alkoxylates based on natural and synthetic alcohols (which may be branched or linear) and prepared from the alcohols and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof; amine ethoxylates, alkanolamides and ethoxylated alkanolamides; alkoxylated triglycerides such as ethoxylated soybean, castor and rapeseed oils; alkylphenol alkoxylates such as octylphenol ethoxylates, nonylphenol ethoxylates, dinonyl phenol ethoxylates and dodecyl phenol ethoxylates (prepared from the phenols and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof); block polymers prepared from ethylene oxide or propylene oxide and reverse block polymers where the terminal blocks are prepared from propylene oxide; ethoxylated fatty acids; ethoxylated fatty esters and oils; ethoxylated methyl esters; ethoxylated tristyrylphenol (including those prepared from ethylene oxide, propylene oxide, butylene oxide or mixtures thereof); fatty acid esters, glycerol esters, lanolin-based derivatives, polyethoxylate esters such as polyethoxylated sorbitan fatty acid esters, polyethoxylated sorbitol fatty acid esters and polyethoxylated glycerol fatty acid esters; other sorbitan derivatives such as sorbitan esters; polymeric surfactants such as random copolymers, block copolymers, alkyd peg (polyethylene glycol) resins, graft or comb polymers and star polymers; polyethylene glycols (pegs); polyethylene glycol fatty acid esters; silicone-based surfactants; and sugar-derivatives such as sucrose esters, alkyl polyglycosides and alkyl polysaccharides.

Useful anionic surfactants include, but are not limited to: alkylaryl sulfonic acids and their salts; carboxylated alcohol or alkylphenol ethoxylates; diphenyl sulfonate derivatives; lignin and lignin derivatives such as lignosulfonates; maleic or succinic acids or their anhydrides; olefin sulfonates; phosphate esters such as phosphate esters of alcohol alkoxylates, phosphate esters of alkylphenol alkoxylates and phosphate esters of styryl phenol ethoxylates; protein-based surfactants; sarcosine derivatives; styryl phenol ether sulfate; sulfates and sulfonates of oils and fatty acids; sulfates and sulfonates of ethoxylated alkylphenols; sulfates of alcohols; sulfates of ethoxylated alcohols; sulfonates of amines and amides such as N,N-alkyltaurates; sulfonates of benzene, cumene, toluene, xylene, and dodecyl and tridecylbenzenes; sulfonates of condensed naphthalenes; sulfonates of naphthalene and alkyl naphthalene; sulfonates of fractionated petroleum; sulfosuccinamates; and sulfosuccinates and their derivatives such as dialkyl sulfosuccinate salts.

Useful cationic surfactants include, but are not limited to: amides and ethoxylated amides; amines such as N-alkyl propanediamines, tripropylenetriamines and dipropylenetetramines, and ethoxylated amines, ethoxylated diamines and propoxylated amines (prepared from the amines and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof); amine salts such as amine acetates and diamine salts; quaternary ammonium salts such as quaternary salts, ethoxylated quaternary salts and diquaternary salts; and amine oxides such as alkyldimethylamine oxides and bis-(2-hydroxyethyl)-alkylamine oxides.

Also useful for the present compositions are mixtures of nonionic and anionic surfactants or mixtures of nonionic and cationic surfactants. Nonionic, anionic and cationic surfactants and their recommended uses are disclosed in a variety of published references including McCutcheon's Emulsifiers and Detergents, annual American and International Editions published by McCutcheon's Division, The Manufacturing Confectioner Publishing Co.; Sisely and Wood, Encyclopedia of Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964; and A. S. Davidson and B. Milwidsky, Synthetic Detergents, Seventh Edition, John Wiley and Sons, New York, 1987.

Compositions of this invention may also contain formulation auxiliaries and additives, known to those skilled in the art as formulation aids (some of which may be considered to also function as solid diluents, liquid diluents or surfactants). Such formulation auxiliaries and additives may control: pH (buffers), foaming during processing (antifoams such polyorganosiloxanes), sedimentation of active ingredients (suspending agents), viscosity (thixotropic thickeners), in-container microbial growth (antimicrobials), product freezing (antifreezes), color (dyes/pigment dispersions), wash-off (film formers or stickers), evaporation (evaporation retardants), and other formulation attributes. Film formers include, for example, polyvinyl acetates, polyvinyl acetate copolymers, polyvinylpyrrolidone-vinyl acetate copolymer, polyvinyl alcohols, polyvinyl alcohol copolymers and waxes. Examples of formulation auxiliaries and additives include those listed in McCutcheon's Volume 2: Functional Materials, annual International and North American editions published by McCutcheon's Division, The Manufacturing Confectioner Publishing Co.; and PCT Publication WO 03/024222.

The compound of Formula 1 and any other active ingredients are typically incorporated into the present compositions by dissolving the active ingredient in a solvent or by grinding in a liquid or dry diluent. Solutions, including emulsifiable concentrates, can be prepared by simply mixing the ingredients. If the solvent of a liquid composition intended for use as an emulsifiable concentrate is water-immiscible, an emulsifier is typically added to emulsify the active-containing solvent upon dilution with water. Active ingredient slurries, with particle diameters of up to 2,000 μm can be wet milled using media mills to obtain particles with average diameters below 3 μm. Aqueous slurries can be made into finished suspension concentrates (see, for example, U.S. Pat. No. 3,060,084) or further processed by spray drying to form water-dispersible granules. Dry formulations usually require dry milling processes, which produce average particle diameters in the 2 to 10 μm range. Dusts and powders can be prepared by blending and usually grinding (such as with a hammer mill or fluid-energy mill). Granules and pellets can be prepared by spraying the active material upon preformed granular carriers or by agglomeration techniques. See Browning, “Agglomeration”, Chemical Engineering, Dec. 4, 1967, pp 147-48, Perry's Chemical Engineer's Handbook, 4th Ed., McGraw-Hill, New York, 1963, pages 8-57 and following, and WO 91/13546. Pellets can be prepared as described in U.S. Pat. No. 4,172,714. Water-dispersible and water-soluble granules can be prepared as taught in U.S. Pat. No. 4,144,050, U.S. Pat. No. 3,920,442 and DE 3,246,493. Tablets can be prepared as taught in U.S. Pat. No. 5,180,587, U.S. Pat. No. 5,232,701 and U.S. Pat. No. 5,208,030. Films can be prepared as taught in GB 2,095,558 and U.S. Pat. No. 3,299,566.

For further information regarding the art of formulation, see T. S. Woods, “The Formulator's Toolbox—Product Forms for Modern Agriculture” in Pesticide Chemistry and Bioscience, The Food-Environment Challenge, T. Brooks and T. R. Roberts, Eds., Proceedings of the 9th International Congress on Pesticide Chemistry, The Royal Society of Chemistry, Cambridge, 1999, pp. 120-133. See also U.S. Pat. No. 3,235,361, Col. 6, line 16 through Col. 7, line 19 and Examples 10-41; U.S. Pat. No. 3,309,192, Col. 5, line 43 through Col. 7, line 62 and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167 and 169-182; U.S. Pat. No. 2,891,855, Col. 3, line 66 through Col. 5, line 17 and Examples 1-4; Klingman, Weed Control as a Science, John Wiley and Sons, Inc., New York, 1961, pp 81-96; Hance et al., Weed Control Handbook, 8th Ed., Blackwell Scientific Publications, Oxford, 1989; and Developments in formulation technology, PJB Publications, Richmond, UK, 2000.

In the following Examples, all percentages are by weight and all formulations are prepared in conventional ways. Compound numbers refer to compounds in Index Tables A-B. Without further elaboration, it is believed that one skilled in the art using the preceding description can utilize the present invention to its fullest extent. The following Examples are, therefore, to be construed as merely illustrative, and not limiting of the disclosure in any way whatsoever. Percentages are by weight except where otherwise indicated.

EXAMPLE A

High Strength Concentrate

Compound 4 98.5% silica aerogel 0.5% synthetic amorphous fine silica 1.0%

EXAMPLE B

Wettable Powder

Compound 4 65.0% dodecylphenol polyethylene glycol ether 2.0% sodium ligninsulfonate 4.0% sodium silicoaluminate 6.0% montmorillonite (calcined) 23.0%

EXAMPLE C

Granule

Compound 4 10.0% attapulgite granules (low volatile matter, 0.71/0.30 mm; 90.0% U.S.S. No. 25-50 sieves)

EXAMPLE D

Extruded Pellet

Compound 4 25.0% anhydrous sodium sulfate 10.0% crude calcium ligninsulfonate 5.0% sodium alkylnaphthalenesulfonate 1.0% calcium/magnesium bentonite 59.0%

EXAMPLE E

Emulsifiable Concentrate

Compound 4 10.0% polyoxyethylene sorbitol hexoleate 20.0% C₆-C₁₀ fatty acid methyl ester 70.0%

EXAMPLE F

Microemulsion

Compound 4 5.0% polyvinylpyrrolidone-vinyl acetate copolymer 30.0% alkylpolyglycoside 30.0% glyceryl monooleate 15.0% water 20.0%

EXAMPLE G

Suspension Concentrate

Compound 4  35% butyl polyoxyethylene/polypropylene block copolymer 4.0% stearic acid/polyethylene glycol copolymer 1.0% styrene acrylic polymer 1.0% xanthan gum 0.1% propylene glycol 5.0% silicone based defoamer 0.1% 1,2-benzisothiazolin-3-one 0.1% water 53.7% 

EXAMPLE H

Emulsion in Water

Compound 4 10.0%  butyl polyoxyethylene/polypropylene block copolymer 4.0% stearic acid/polyethylene glycol copolymer 1.0% styrene acrylic polymer 1.0% xanthan gum 0.1% propylene glycol 5.0% silicone based defoamer 0.1% 1,2-benzisothiazolin-3-one 0.1% aromatic petroleum based hydrocarbon 20.0 Water 58.7% 

EXAMPLE I

Oil Dispersion

Compound 4 25% polyoxyethylene sorbitol hexaoleate 15% organically modified bentonite clay 2.5%  fatty acid methyl ester 57.5% 

The present disclosure also includes Examples A through I above except “Compound 4” is replaced with “Compound 2”, “Compound 3”, “Compound 5”, “Compound 6”, “Compound 7”, “Compound 8”, “Compound 9”, “Compound 10”, “Compound 11”, “Compound 12”, “Compound 13”, “Compound 14”, “Compound 15”, “Compound 16”, “Compound 17”, “Compound 18”, “Compound 19”, “Compound 20”, “Compound 21”, “Compound 22”, “Compound 23”, “Compound 24”, “Compound 25”, “Compound 26”, “Compound 27”, “Compound 28”, “Compound 29”, “Compound 30”, “Compound 31”, “Compound 32”, “Compound 33”, “Compound 34”, “Compound 35”, “Compound 36”, “Compound 37”, “Compound 38”, “Compound 39”, “Compound 40”, “Compound 41”, “Compound 42”, “Compound 43”, “Compound 44”, “Compound 45”, “Compound 46”, “Compound 47”, “Compound 48”, “Compound 49”, “Compound 50”, “Compound 51”, “Compound 52”, “Compound 53”, “Compound 54”, “Compound 55”, “Compound 56”, “Compound 57”, “Compound 58”, “Compound 59”, “Compound 60”, “Compound 61”, “Compound 62”, “Compound 63”, “Compound 64”, “Compound 65”, “Compound 66”, “Compound 67”, “Compound 68”, “Compound 69”, “Compound 70”, “Compound 71”, “Compound 72”, “Compound 73”, “Compound 74”, “Compound 75”, “Compound 76”, “Compound 77” or “Compound 78”.

Test results indicate that the compounds of the present invention are highly active preemergent and/or postemergent herbicides and/or plant growth regulants. The compounds of the Mention generally show highest activity for postemergence weed control (i.e. applied after weed seedlings emerge from the soil) and preemergence weed control (i.e. applied before weed seedlings emerge from the soil). Many of them have utility for broad-spectrum pre- and/or postemergence weed control in areas where complete control of all vegetation is desired such as around fuel storage tanks, industrial storage areas, parking lots, drive-in theaters, air fields, river banks, irrigation and other waterways, around billboards and highway and railroad structures. Many of the compounds of this invention, by virtue of selective metabolism in crops versus weeds, or by selective activity at the locus of physiological inhibition in crops and weeds, or by selective placement on or within the environment of a mixture of crops and weeds, are useful for the selective control of grass and broadleaf weeds within a crop/weed mixture. One skilled in the art will recognize that the preferred combination of these selectivity factors within a compound or group of compounds can readily be determined by performing routine biological and/or biochemical assays. Compounds of this invention may show tolerance to important agronomic crops including, but is not limited to, alfalfa, barley, cotton, wheat, rape, sugar beets, corn (maize), sorghum, soybeans, rice, oats, peanuts, vegetables, tomato, potato, perennial plantation crops including coffee, cocoa, oil palm, rubber, sugarcane, citrus, grapes, fruit trees, nut trees, banana, plantain, pineapple, hops, tea and forests such as eucalyptus and conifers (e.g., loblolly pine), and turf species (e.g., Kentucky bluegrass, St. Augustine grass, Kentucky fescue and Bermuda grass). Compounds of this invention can be used in crops genetically transformed or bred to incorporate resistance to herbicides, express proteins toxic to invertebrate pests (such as Bacillus thuringiensis toxin), and/or express other useful traits. Those skilled in the art will appreciate that not all compounds are equally effective against all weeds. Alternatively, the subject compounds are useful to modify plant growth.

As the compounds of the invention have both preemergent and postemergent herbicidal activity, to control undesired vegetation by killing or injuring the vegetation or reducing its growth, the compounds can be usefully applied by a variety of methods involving contacting a herbicidally effective amount of a compound of the invention, or a composition comprising said compound and at least one of a surfactant, a solid diluent or a liquid diluent, to the foliage or other part of the undesired vegetation or to the environment of the undesired vegetation such as the soil or water in which the undesired vegetation is growing or which surrounds the seed or other propagule of the undesired vegetation.

A herbicidally effective amount of the compounds of this invention is determined by a number of factors. These factors include: formulation selected, method of application, amount and type of vegetation present, growing conditions, etc. In general, a herbicidally effective amount of compounds of this invention is about 0.001 to 20 kg/ha with a preferred range of about 0.004 to 1 kg/ha. One skilled in the art can easily determine the herbicidally effective amount necessary for the desired level of weed control.

In one common embodiment, a compound of the invention is applied, typically in a formulated composition, to a locus comprising desired vegetation (e.g., crops) and undesired vegetation (i.e. weeds), both of which may be seeds, seedlings and/or larger plants, in contact with a growth medium (e.g., soil). In this locus, a composition comprising a compound of the invention can be directly applied to a plant or a part thereof, particularly of the undesired vegetation, and/or to the growth medium in contact with the plant.

Plant varieties and cultivars of the desired vegetation in the locus treated with a compound of the invention can be obtained by conventional propagation and breeding methods or by genetic engineering methods. Genetically modified plants (transgenic plants) are those in which a heterologous gene (transgene) has been stably integrated into the plant's genome. A transgene that is defined by its particular location in the plant genome is called a transformation or transgenic event.

Genetically modified plant cultivars in the locus which can be treated according to the invention include those that are resistant against one or more biotic stresses (pests such as nematodes, insects, mites, fungi, etc.) or abiotic stresses (drought, cold temperature, soil salinity, etc.), or that contain other desirable characteristics. Plants can be genetically modified to exhibit traits of, for example, herbicide tolerance, insect-resistance, modified oil profiles or drought tolerance. Useful genetically modified plants containing single gene transformation events or combinations of transformation events are listed in Exhibit C. Additional information for the genetic modifications listed in Exhibit C can be obtained from publicly available databases maintained, for example, by the U.S. Department of Agriculture.

The following abbreviations, T1 through T37, are used in Exhibit C for traits. A “−” means the entry is not available; “tol.” means “tolerance” and “res.” means resistance.

Trait Description T1 Glyphosate tol. T2 High lauric acid oil T3 Glufosinate tol. T4 Phytate breakdown T5 Oxynil tol. T6 Disease res. T7 Insect res. T9 Modified flower color T11 ALS Herbicide tol. T12 Dicamba tol. T13 Anti-allergy T14 Salt tol. T15 Cold tol. T16 Imidazolinone herb. tol. T17 Modified alpha-amylase T18 Pollination control T19 2,4-D tol. T20 Increased lysine T21 Drought tol. T22 Delayed ripening/senescence T23 Modified product quality T24 High cellulose T25 Modified starch/carbohydrate T26 Insect & disease resist. T27 High tryptophan T28 Erect leaves semidwarf T29 Semidwarf T30 Low iron tol. T31 Modified oil/fatty acid T32 HPPD tol. T33 High oil T34 Aryloxyalkanoate tol. T35 Mesotrione tol. T36 Reduced nicotine T37 Modified product

Exhibit C

Crop Event Name Event Code Trait(s) Gene(s) Alfalfa J101 MON-00101-8 T1 cp4 epsps (aroA:CP4) Alfalfa J163 MON-ØØ163-7 T1 cp4 epsps (aroA:CP4) Canola* 23-18-17 (Event 18) CGN-89465-2 T2 te Canola* 23-198 (Event 23) CGN-89465-2 T2 te Canola* 61061 DP-Ø61Ø61-7 T1 gat4621 Canola* 73496 DP-Ø73496-4 T1 gat4621 Canola* GT200 (RT200) MON-89249-2 T1 cp4 epsps (aroA:CP4); goxv247 Canola* GT73 (RT73) MON-ØØØ73-7 T1 cp4 epsps (aroA:CP4); goxv247 Canola* HCN10 (Topas 19/2) — T3 bar Canola* HCN28 (T45) ACS-BNØØ8-2 T3 pat (syn) Canola* HCN92 (Topas 19/2) ACS-BNØØ7-1 T3 bar Canola* MON88302 MON-883Ø2-9 T1 cp4 epsps (aroA:CP4) Canola* MPS961 — T4 phyA Canola* MPS962 — T4 phyA Canola* MPS963 — T4 phyA Canola* MPS964 — T4 phyA Canola* MPS965 — T4 phyA Canola* MS1 (B91-4) ACS-BNØØ4-7 T3 bar Canola* MS8 ACS-BNØØ5-8 T3 bar Canola* OXY-235 ACS-BNØ11-5 T5 bxn Canola* PHY14 — T3 bar Canola* PHY23 — T3 bar Canola* PHY35 — T3 bar Canola* PHY36 — T3 bar Canola* RF1 (B93-101) ACS-BNØØ1-4 T3 bar Canola* RF2 (B94-2) ACS-BNØØ2-5 T3 bar Canola* RF3 ACS-BNØØ3-6 T3 bar Bean EMBRAPA 5.1 EMB-PV051-1 T6 ac1 (sense and antisense) Brinjal # EE-1 — T7 cry1Ac Cotton 19-51a DD-Ø1951A-7 T11 S4-HrA Cotton 281-24-236 DAS-24236-5 T3, T7 pat (syn); cry1F Cotton 3006-210-23 DAS-21Ø23-5 T3, T7 pat (syn); cry1Ac Cotton 31707 — T5, T7 bxn; cry1Ac Cotton 31803 — T5, T7 bxn; cry1Ac Cotton 31807 — T5, T7 bxn; cry1Ac Cotton 31808 — T5, T7 bxn; cry1Ac Cotton 42317 — T5, T7 bxn; cry1Ac Cotton BNLA-601 — T7 cry1Ac Cotton BXN10211 BXN10211-9 T5 bxn; cry1Ac Cotton BXN10215 BXN10215-4 T5 bxn; cry1Ac Cotton BXN10222 BXN10222-2 T5 bxn; cry1Ac Cotton BXN10224 BXN10224-4 T5 bxn; cry1Ac Cotton COT102 SYN-IR102-7 T7 vip3A(a) Cotton COT67B SYN-IR67B-1 T7 cry1Ab Cotton COT202 — T7 vip3A Cotton Event 1 — T7 cry1Ac Cotton GMF Cry1A GTL-GMF311-7 T7 cry1Ab-Ac Cotton GHB119 BCS-GH005-8 T7 cry2Ae Cotton GHB614 BCS-GH002-5 T1 2mepsps Cotton GK12 — T7 cry1Ab-Ac Cotton LLCotton25 ACS-GH001-3 T3 bar Cotton MLS 9124 — T7 cry1C Cotton MON1076 MON-89924-2 T7 cry1Ac Cotton MON1445 MON-01445-2 T1 cp4 epsps (aroA:CP4) Cotton MON15985 MON-15985-7 T7 cry1Ac; cry2Ab2 Cotton MON1698 MON-89383-1 T7 cp4 epsps (aroA:CP4) Cotton MON531 MON-00531-6 T7 cry1Ac Cotton MON757 MON-00757-7 T7 cry1Ac Cotton MON88913 MON-88913-8 T1 cp4 epsps (aroA:CP4) Cotton Nqwe Chi 6 Bt — T7 — Cotton SKG321 — T7 cry1A; CpTI Cotton T303-3 BCS-GH003-6 T3, T7 cry1Ab; bar Cotton T304-40 BCS-GH004-7 T3, T7 cry1Ab; bar Cotton CE43-67B — T7 cry1Ab Cotton CE46-02A — T7 cry1Ab Cotton CE44-69D — T7 cry1Ab Cotton 1143-14A — T7 cry1Ab Cotton 1143-51B — T7 cry1Ab Cotton T342-142 — T7 cry1Ab Cotton PV-GHGT07 (1445) — T1 cp4 epsps (aroA:CP4) Cotton EE-GH3 — T1 mepsps Cotton EE-GH5 — T7 cry1Ab Cotton MON88701 MON-88701-3 T3, T12 Modified dmo; bar Cotton OsCr11 — T13 Modified Cry j Flax FP967 CDC-FL001-2 T11 als Lentil RH44 — T16 als Maize 3272 SYN-E3272-5 T17 amy797E Maize 5307 SYN-05307-1 T7 ecry3.1Ab Maize 59122 DAS-59122-7 T3, T7 cry34Ab1; cry35Ab1; pat Maize 676 PH-000676-7 T3, T18 pat; dam Maize 678 PH-000678-9 T3, T18 pat; dam Maize 680 PH-000680-2 T3, T18 pat; dam Maize 98140 DP-098140-6 T1, T11 gat4621; zm-hra Maize Bt10 — T3, T7 cry1Ab; pat Maize Bt176 (176) SYN-EV176-9 T3, T7 cry1Ab; bar Maize BVLA430101 — T4 phyA2 Maize CBH-351 ACS-ZM004-3 T3, T7 cry9C; bar Maize DAS40278-9 DAS40278-9 T19 aad-1 Maize DBT418 DKB-89614-9 T3, T7 cry1Ac; pinII; bar Maize DLL25 (B16) DKB-89790-5 T3 bar Maize GA21 MON-00021-9 T1 mepsps Maize GG25 — T1 mepsps Maize GJ11 — T1 mepsps Maize Fl117 — T1 mepsps Maize GAT-ZM1 — T3 pat Maize LY038 REN-00038-3 T20 cordapA Maize MIR162 SYN-IR162-4 T7 vip3Aa20 Maize MIR604 SYN-IR604-5 T7 mcry3A Maize MON801 (MON80100) MON801 T1, T7 cry1Ab; cp4 epsps (aroA:CP4); goxv247 Maize MON802 MON-80200-7 T1, T7 cry1Ab; cp4 epsps (aroA:CP4); goxv247 Maize MON809 PH-MON-809-2 T1, T7 cry1Ab; cp4 epsps (aroA:CP4); goxv247 Maize MON810 MON-00810-6 T1, T7 cry1Ab; cp4 epsps (aroA:CP4); goxv247 Maize MON832 — T1 cp4 epsps (aroA:CP4); goxv247 Maize MON863 MON-00863-5 T7 cry3Bb1 Maize MON87427 MON-87427-7 T1 cp4 epsps (aroA:CP4) Maize MON87460 MON-87460-4 T21 cspB Maize MON88017 MON-88017-3 T1, T7 cry3Bb1; cp4 epsps (aroA:CP4) Maize MON89034 MON-89034-3 T7 cry2Ab2; cry1A.105 Maize MS3 ACS-ZM001-9 T3, T18 bar; barnase Maize MS6 ACS-ZM005-4 T3, T18 bar; barnase Maize NK603 MON-00603-6 T1 cp4 epsps (aroA:CP4) Maize T14 ACS-ZM002-1 T3 pat (syn) Maize T25 ACS-ZM003-2 T3 pat (syn) Maize TC1507 DAS-01507-1 T3, T7 cry1Fa2; pat Maize TC6275 DAS-06275-8 T3, T7 mocry1F; bar Maize VIP1034 — T3, T7 vip3A; pat Maize 43A47 DP-043A47-3 T3, T7 cry1F; cry34Ab1; cry35Ab1; pat Maize 40416 DP-040416-8 T3, T7 cry1F; cry34Ab1; cry35Ab1; pat Maize 32316 DP-032316-8 T3, T7 cry1F; cry34Ab1; cry35Ab1; pat Maize 4114 DP-004114-3 T3, T7 cry1F; cry34Ab1; cry35Ab1; pat Melon Melon A — T22 sam-k Melon Melon B — T22 sam-k Papaya 55-1 CUH-CP551-8 T6 prsv cp Papaya 63-1 CUH-CP631-7 T6 prsv cp Papaya Huanong No. 1 — T6 prsv rep Papaya X17-2 UFL-X17CP-6 T6 prsv cp Plum C-5 ARS-PLMC5-6 T6 ppv cp Canola** ZSR500 — T1 cp4 epsps (aroA:CP4); goxv247 Canola** ZSR502 — T1 cp4 epsps (aroA:CP4); goxv247 Canola** ZSR503 — T1 cp4 epsps (aroA:CP4); goxv247 Rice 7Crp#242-95-7 — T13 7crp Rice 7Crp#10 — T13 7crp Rice GM Shanyou 63 — T7 cry1Ab; cry1Ac Rice Huahui-1/TT51-1 — T7 cry1Ab; cry1Ac Rice LLRICE06 ACS-OS001-4 T3 bar Rice LLRICE601 BCS-OS003-7 T3 bar Rice LLRICE62 ACS-OS002-5 T3 bar Rice Tarom molaii + cry1Ab — T7 cry1Ab (truncated) Rice GAT-OS2 — T3 bar Rice GAT-OS3 — T3 bar Rice PE-7 — T7 Cry1Ac Rice 7Crp#10 — T13 7crp Rice KPD627-8 — T27 OASA1D Rice KPD722-4 — T27 OASA1D Rice KA317 — T27 OASA1D Rice HW5 — T27 OASA1D Rice HW1 — T27 OASA1D Rice B-4-1-18 — T28 Δ OsBRI1 Rice G-3-3-22 — T29 OSGA2ox1 Rice AD77 — T6 DEF Rice AD51 — T6 DEF Rice AD48 — T6 DEF Rice AD41 — T6 DEF Rice 13pNasNa800725atAprt1 — T30 HvNAS1; HvNAAT-A; APRT Rice 13pAprt1 — T30 APRT Rice gHvNAS1-gHvNAAT-1 — T30 HvNAS1; HvNAAT-A; HvNAAT-B Rice gHvIDS3-1 — T30 HvIDS3 Rice gHvNAAT1 — T30 HvNAAT-A; HvNAAT-B Rice gHvNAS1-1 — T30 HvNAS1 Rice NIA-OS006-4 — T6 WRKY45 Rice NIA-OS005-3 — T6 WRKY45 Rice NIA-OS004-2 — T6 WRKY45 Rice NIA-OS003-1 — T6 WRKY45 Rice NIA-OS002-9 — T6 WRKY45 Rice NIA-OS001-8 — T6 WRKY45 Rice OsCr11 — T13 Modified Cry j Rice 17053 — T1 cp4 epsps (aroA:CP4) Rice 17314 — T1 cp4 epsps (aroA:CP4) Rose WKS82/130-4-1 IFD-52401-4 T9 5AT; bp40 (f3′5′h) Rose WKS92/130-9-1 IFD-52901-9 T9 5AT; bp40 (f3′5′h) Soybean 260-05 (G94-1, G94-19, — T9 gm-fad2-1 (silencing locus) G168) Soybean A2704-12 ACS-GM005-3 T3 pat Soybean A2704-21 ACS-GM004-2 T3 pat Soybean A5547-127 ACS-GM006-4 T3 pat Soybean A5547-35 ACS-GM008-6 T3 pat Soybean CV127 BPS-CV127-9 T16 csr1-2 Soybean DAS68416-4 DAS68416-4 T3 pat Soybean DP305423 DP-305423-1 T11, T31 gm-fad2-1 (silencing locus); gm-hra Soybean DP356043 DP-356043-5 T1, T31 gm-fad2-1 (silencing locus); gat4601 Soybean FG72 MST-FG072-3 T32, T1 2mepsps; hppdPF W336 Soybean GTS 40-3-2 (40-3-2) MON-04032-6 T1 cp4 epsps (aroA:CP4) Soybean GU262 ACS-GM003-1 T3 pat Soybean MON87701 MON-87701-2 T7 cry1Ac Soybean MON87705 MON-87705-6 T1, T31 fatb1-A (sense & antisense); fad2-1A (sense & antisense); cp4 epsps (aroA:CP4) Soybean MON87708 MON-87708-9 T1, T12 dmo; cp4 epsps (aroA:CP4) Soybean MON87769 MON-87769-7 T1, T31 Pj.D6D; Nc.Fad3; cp4 epsps (aroA:CP4) Soybean MON89788 MON-89788-1 T1 cp4 epsps (aroA:CP4) Soybean W62 ACS-GM002-9 T3 bar Soybean W98 ACS-GM001-8 T3 bar Soybean MON87754 MON-87754-1 T33 dgat2A Soybean DAS21606 DAS-21606 T34, T3 Modified aad-12; pat Soybean DAS44406 DAS-44406-6 T1, T3, T34 Modified aad-12; 2mepsps; pat Soybean SYHT04R SYN-0004R-8 T35 Modified avhppd Soybean 9582.814.19.1 — T3, T7 cry1Ac, cry1F, PAT Squash CZW3 SEM-ØCZW3-2 T6 cmv cp, zymv cp, wmv cp Squash ZW20 SEM-0ZW20-7 T6 zymv cp, wmv cp Sugar Beet GTSB77 (T9100152) SY-GTSB77-8 T1 cp4 epsps (aroA:CP4); goxv247 Sugar Beet H7-1 KM-000H71-4 T1 cp4 epsps (aroA:CP4) Sugar Beet T120-7 ACS-BV001-3 T3 pat Sugar Beet T227-1 — T1 cp4 epsps (aroA:CP4) Sugarcane NXI-1T — T21 EcbetA Sunflower X81359 — T16 als Pepper PK-SP01 — T6 cmv cp Tobacco C/F/93/08-02 — T5 bxn Tobacco Vector 21-41 — T36 NtQPT1 (antisense) Sunflower X81359 — T16 als Wheat MON71800 MON-718ØØ-3 T1 cp4 epsps (aroA:CP4) *Argentine (Brassica napus), **Polish (B. rapa), # Eggplant

Although most typically, compounds of the invention are used to control undesired vegetation, contact of desired vegetation in the treated locus with compounds of the invention may result in super-additive or synergistic effects with genetic traits in the desired vegetation, including traits incorporated through genetic modification. For example, resistance to phytophagous insect pests or plant diseases, tolerance to biotic/abiotic stresses or storage stability may be greater than expected from the genetic traits in the desired vegetation.

An embodiment of the present invention is a method for controlling the growth of undesired vegetation in genetically modified plants that exhibit traits of glyphosate tolerance, glufosinate tolerance, ALS herbicide tolerance, dicamba tolerance, imidazolinone herbicide tolerance, 2,4-D tolerance, HPPD tolerance and mesotrione tolerance, comprising contacting the vegetation or its environment with a herbicidally effective amount of a compound of Formula 1.

Compounds of this invention can also be mixed with one or more other biologically active compounds or agents including herbicides, herbicide safeners, fungicides, insecticides, nematocides, bactericides, acaricides, growth regulators such as insect molting inhibitors and rooting stimulants, chemosterilants, semiochemicals, repellents, attractants, pheromones, feeding stimulants, plant nutrients, other biologically active compounds or entomopathogenic bacteria, virus or fungi to form a multi-component pesticide giving an even broader spectrum of agricultural protection. Mixtures of the compounds of the invention with other herbicides can broaden the spectrum of activity against additional weed species, and suppress the proliferation of any resistant biotypes. Thus the present invention also pertains to a composition comprising a compound of Formula 1 (in a herbicidally effective amount) and at least one additional biologically active compound or agent (in a biologically effective amount) and can further comprise at least one of a surfactant, a solid diluent or a liquid diluent. The other biologically active compounds or agents can be formulated in compositions comprising at least one of a surfactant, solid or liquid diluent. For mixtures of the present invention, one or more other biologically active compounds or agents can be formulated together with a compound of Formula 1, to form a premix, or one or more other biologically active compounds or agents can be formulated separately from the compound of Formula 1, and the formulations combined together before application (e.g., in a spray tank) or, alternatively, applied in succession.

A mixture of one or more of the following herbicides with a compound of this invention may be particularly useful for weed control: acetochlor, acifluorfen and its sodium salt, aclonifen, acrolein (2-propenal), alachlor, alloxydim, ametryn, amicarbazone, amidosulfuron, aminocyclopyrachlor and its esters (e.g., methyl, ethyl) and salts (e.g., sodium, potassium), aminopyralid, amitrole, ammonium sulfamate, anilofos, asulam, atrazine, azimsulfuron, beflubutamid, benazolin, benazolin-ethyl, bencarbazone, benfluralin, benfuresate, bensulfuron-methyl, bensulide, bentazone, benzobicyclon, benzofenap, bicyclopyrone, bifenox, bilanafos, bispyribac and its sodium salt, bromacil, bromobutide, bromofenoxim, bromoxynil, bromoxynil octanoate, butachlor, butafenacil, butamifos, butralin, butroxydim, butylate, cafenstrole, carbetamide, carfentrazone-ethyl, catechin, chlomethoxyfen, chloramben, chlorbromuron, chlorflurenol-methyl, chloridazon, chlorimuron-ethyl, chlorotoluron, chlorpropham, chlorsulfuron, chlorthal-dimethyl, chlorthiamid, cinidon-ethyl, cinmethylin, cinosulfuron, clacyfos, clefoxydim, clethodim, clodinafop-propargyl, clomazone, clomeprop, clopyralid, clopyralid-olamine, cloransulam-methyl, cumyluron, cyanazine, cycloate, cyclopyrimorate, cyclosulfamuron, cycloxydim, cyhalofop-butyl, 2,4-D and its butotyl, butyl, isoctyl and isopropyl esters and its dimethylammonium, diolamine and trolamine salts, daimuron, dalapon, dalapon-sodium, dazomet, 2,4-DB and its dimethylammonium, potassium and sodium salts, desmedipham, desmetryn, dicamba and its diglycolammonium, dimethylammonium, potassium and sodium salts, dichlobenil, dichlorprop, diclofop-methyl, diclosulam, difenzoquat metilsulfate, diflufenican, diflufenzopyr, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethenamid, dimethenamid-P, dimethipin, dimethylarsinic acid and its sodium salt, dinitramine, dinoterb, diphenamid, diquat dibromide, dithiopyr, diuron, DNOC, endothal, EPTC, esprocarb, ethalfluralin, ethametsulfuron-methyl, ethiozin, ethofumesate, ethoxyfen, ethoxysulfuron, etobenzanid, fenoxaprop-ethyl, fenoxaprop-P-ethyl, fenoxasulfone, fenquinotrione, fentrazamide, fenuron, fenuron-TCA, flamprop-methyl, flamprop-M-isopropyl, flamprop-M-methyl, flazasulfuron, florasulam, fluazifop-butyl, fluazifop-P-butyl, fluazolate, flucarbazone, flucetosulfuron, fluchloralin, flufenacet, flufenpyr, flufenpyr-ethyl, flumetsulam, flumiclorac-pentyl, flumioxazin, fluometuron, fluoroglycofen-ethyl, flupoxam, flupyrsulfuron-methyl and its sodium salt, flurenol, flurenol-butyl, fluridone, flurochloridone, fluroxypyr, flurtamone, fluthiacet-methyl, fomesafen, foramsulfuron, fosamine-ammonium, glufosinate, glufosinate-ammonium, glufosinate-P, glyphosate and its salts such as ammonium, isopropylammonium, potassium, sodium (including sesquisodium) and trimesium (alternatively named sulfosate), halauxifen, halauxifen-methyl, halosulfuron-methyl, haloxyfop-etotyl, haloxyfop-methyl, hexazinone, hydantocidin, imazamethabenz-methyl, imazamox, imazapic, imazapyr, imazaquin, imazaquin-ammonium, imazethapyr, imazethapyr-ammonium, imazosulfuron, indanofan, indaziflam, iofensulfuron, iodosulfuron-methyl, ioxynil, ioxynil octanoate, ioxynil-sodium, ipfencarbazone, isoproturon, isouron, isoxaben, isoxaflutole, isoxachlortole, lactofen, lenacil, linuron, maleic hydrazide, MCPA and its salts (e.g., MCPA-dimethylammonium, MCPA-potassium and MCPA-sodium, esters (e.g., MCPA-2-ethylhexyl, MCPA-butotyl) and thioesters (e.g., MCPA-thioethyl), MCPB and its salts (e.g., MCPB-sodium) and esters (e.g., MCPB -ethyl), mecoprop, mecoprop-P, mefenacet, mefluidide, mesosulfuron-methyl, mesotrione, metam-sodium, metamifop, metamitron, metazachlor, metazosulfuron, methabenzthiazuron, methylarsonic acid and its calcium, monoammonium, monosodium and disodium salts, methyldymron, metobenzuron, metobromuron, metolachlor, S-metolachlor, metosulam, metoxuron, metribuzin, metsulfuron-methyl, molinate, monolinuron, naproanilide, napropamide, napropamide-M, naptalam, neburon, nicosulfuron, norflurazon, orbencarb, orthosulfamuron, oryzalin, oxadiargyl, oxadiazon, oxasulfuron, oxaziclomefone, oxyfluorfen, paraquat dichloride, pebulate, pelargonic acid, pendimethalin, penoxsulam, pentanochlor, pentoxazone, perfluidone, pethoxamid, pethoxyamid, phenmedipham, picloram, picloram-potassium, picolinafen, pinoxaden, piperophos, pretilachlor, primisulfuron-methyl, prodiamine, profoxydim, prometon, prometryn, propachlor, propanil, propaquizafop, propazine, propham, propisochlor, propoxycarbazone, propyrisulfuron, propyzamide, prosulfocarb, prosulfuron, pyraclonil, pyraflufen-ethyl, pyrasulfotole, pyrazogyl, pyrazolynate, pyrazoxyfen, pyrazosulfuron-ethyl, pyribenzoxim, pyributicarb, pyridate, pyriftalid, pyriminobac-methyl, pyrimisulfan, pyrithiobac, pyrithiobac-sodium, pyroxasulfone, pyroxsulam, quinclorac, quinmerac, quinoclamine, quizalofop-ethyl, quizalofop-P-ethyl, quizalofop-P-tefuryl, rimsulfuron, saflufenacil, sethoxydim, siduron, simazine, simetryn, sulcotrione, sulfentrazone, sulfometuron-methyl, sulfosulfuron, 2,3,6-TBA, TCA, TCA-sodium, tebutam, tebuthiuron, tefuryltrione, tembotrione, tepraloxydim, terbacil, terbumeton, terbuthylazine, terbutryn, thenylchlor, thiazopyr, thiencarbazone, thifensulfuron-methyl, thiobencarb, tiafenacil, tiocarbazil, tolpyralate, topramezone, tralkoxydim, tri-allate, triafamone, triasulfuron, triaziflam, tribenuron-methyl, triclopyr, triclopyr-butotyl, triclopyr-triethylammonium, tridiphane, trietazine, trifloxysulfuron, trifludimoxazin, trifluralin, triflusulfuron-methyl, tritosulfuron, vernolate, 3-(2-chloro-3,6-difluorophenyl)-4-hydroxy-1-methyl-1,5-naphthyridin-2(1H)-one, 5-chloro-3-[(2-hydroxy-6-oxo-1-cyclohexen-1-yl)carbonyl]-1-(4-methoxyphenyl)-2(1H)-quinoxalinone, 2-chloro-N-(1-methyl-1H-tetrazol-5-yl)-6-(trifluoromethyl)-3-pyridinecarboxamide, 7-(3,5-dichloro-4-pyridinyl)-5-(2,2-difluoroethyl)-8-hydroxypyrido[2,3-b]pyrazin-6(5H)-one), 4-(2,6-diethyl-4-methylphenyl)-5-hydroxy-2,6-dimethyl-3(2H)-pyridazinone), 5-[[(2,6-difluorophenyl)methoxy]methyl]-4,5-dihydro-5-methyl-3-(3-methyl-2-thienyl)isoxazole (previously methioxolin), 4-(4-fluorophenyl)-6-[(2-hydroxy-6-oxo-1-cyclohexen-1-yl)carbonyl]-2-methyl-1,2,4-triazine-3,5(2H,4H)-dione, methyl 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)-5-fluoro-2-pyridinecarboxylate, 2-methyl-3-(methylsulfonyl)-N-(1-methyl-1H-tetrazol-5-yl)-4-(trifluoromethyl)benzamide and 2-methyl-N-(4-methyl-1,2,5-oxadiazol-3-yl)-3-(methylsulfinyl)-4-(trifluoromethyl)benzamide. Other herbicides also include bioherbicides such as Alternaria destruens Simmons, Colletotrichum gloeosporiodes (Penz.) Penz. & Sacc., Drechsiera monoceras (MTB-951), Myrothecium verrucaria (Albertini & Schweinitz) Ditmar: Fries, Phytophthora palmivora (Butl.) Butl. and Puccinia thlaspeos Schub.

Compounds of this invention can also be used in combination with plant growth regulators such as aviglycine, N-(phenylmethyl)-1H-purin-6-amine, epocholeone, gibberellic acid, gibberellin A₄ and A₇, harpin protein, mepiquat chloride, prohexadione calcium, prohydrojasmon, sodium nitrophenolate and trinexapac-methyl, and plant growth modifying organisms such as Bacillus cereus strain BP01.

General references for agricultural protectants (i.e. herbicides, herbicide safeners, insecticides, fungicides, nematocides, acaricides and biological agents) include The Pesticide Manual, 13th Edition, C. D. S. Tomlin, Ed., British Crop Protection Council, Farnham, Surrey, U.K., 2003 and The BioPesticide Manual, 2nd Edition, L. G. Copping, Ed., British Crop Protection Council, Farnham, Surrey, U.K., 2001.

For embodiments where one or more of these various mixing partners are used, the mixing partners are typically used in the amounts similar to amounts customary when the mixture partners are used alone. More particularly in mixtures, active ingredients are often applied at an application rate between one-half and the full application rate specified on product labels for use of active ingredient alone. These amounts are listed in references such as The Pesticide Manual and The BioPesticide Manual. The weight ratio of these various mixing partners (in total) to the compound of Formula 1 is typically between about 1:3000 and about 3000:1. Of note are weight ratios between about 1:300 and about 300:1 (for example ratios between about 1:30 and about 30:1). One skilled in the art can easily determine through simple experimentation the biologically effective amounts of active ingredients necessary for the desired spectrum of biological activity. It will be evident that including these additional components may expand the spectrum of weeds controlled beyond the spectrum controlled by the compound of Formula 1 alone.

In certain instances, combinations of a compound of this invention with other biologically active (particularly herbicidal) compounds or agents (i.e. active ingredients) can result in a greater-than-additive (i.e. synergistic) effect on weeds and/or a less-than-additive effect (i.e. safening) on crops or other desirable plants. Reducing the quantity of active ingredients released in the environment while ensuring effective pest control is always desirable. Ability to use greater amounts of active ingredients to provide more effective weed control without excessive crop injury is also desirable. When synergism of herbicidal active ingredients occurs on weeds at application rates giving agronomically satisfactory levels of weed control, such combinations can be advantageous for reducing crop production cost and decreasing environmental load. When safening of herbicidal active ingredients occurs on crops, such combinations can be advantageous for increasing crop protection by reducing weed competition.

Of note is a combination of a compound of the invention with at least one other herbicidal active ingredient. Of particular note is such a combination where the other herbicidal active ingredient has different site of action from the compound of the invention. In certain instances, a combination with at least one other herbicidal active ingredient having a similar spectrum of control but a different site of action will be particularly advantageous for resistance management. Thus, a composition of the present invention can further comprise (in a herbicidally effective amount) at least one additional herbicidal active ingredient having a similar spectrum of control but a different site of action.

Compounds of this invention can also be used in combination with herbicide safeners such as allidochlor, benoxacor, cloquintocet-mexyl, cumyluron, cyometrinil, cyprosulfonamide, daimuron, dichlormid, dicyclonon, dietholate, dimepiperate, fenchlorazole-ethyl, fenclorim, flurazole, fluxofenim, furilazole, isoxadifen-ethyl, mefenpyr-diethyl, mephenate, methoxyphenone naphthalic anhydride (1,8-naphthalic anhydride), oxabetrinil, N-(aminocarbonyl)-2-methylbenzenesulfonamide, N-(aminocarbonyl)-2-fluorobenzenesulfonamide, 1-bromo-4-[(chloromethyl)sulfonyl]benzene (BCS), 4-(dichloroacetyl)-1-oxa-4-azospiro[4.5]decane (MON 4660), 2-(dichloromethyl)-2-methyl-1,3-dioxolane (MG 191), ethyl 1,6-dihydro-1-(2-methoxyphenyl)-6-oxo-2-phenyl-5-pyrimidinecarboxylate, 2-hydroxy-N,N-dimethyl-6-(trifluoromethyl)pyridine-3-carboxamide, and 3-oxo-1-cyclohexen-1-yl 1-(3,4-dimethylphenyl)-1,6-dihydro-6-oxo-2-phenyl-5-pyrimidinecarboxylate, 2,2-dichloro-1-(2,2,5-trimethyl-3-oxazolidinyl)-ethanone and 2-methoxy-N-[[4-[[methylamino)carbonyl]amino]phenyl]sulfonyl]-benzamide to increase safety to certain crops. Antidotally effective amounts of the herbicide safeners can be applied at the same time as the compounds of this invention, or applied as seed treatments. Therefore an aspect of the present invention relates to a herbicidal mixture comprising a compound of this invention and an antidotally effective amount of a herbicide safener. Seed treatment is particularly useful for selective weed control, because it physically restricts antidoting to the crop plants. Therefore a particularly useful embodiment of the present invention is a method for selectively controlling the growth of undesired vegetation in a crop comprising contacting the locus of the crop with a herbicidally effective amount of a compound of this invention wherein seed from which the crop is grown is treated with an antidotally effective amount of safener. Antidotally effective amounts of safeners can be easily determined by one skilled in the art through simple experimentation.

Compounds of the invention cans also be mixed with: (1) polynucleotides including but not limited to DNA, RNA, and/or chemically modified nucleotides influencing the amount of a particular target through down regulation, interference, suppression or silencing of the genetically derived transcript that render a herbicidal effect; or (2) polynucleotides including but not limited to DNA, RNA, and/or chemically modified nucleotides influencing the amount of a particular target through down regulation, interference, suppression or silencing of the genetically derived transcript that render a safening effect.

Of note is a composition comprising a compound of the invention (in a herbicidally effective amount), at least one additional active ingredient selected from the group consisting of other herbicides and herbicide safeners (in an effective amount), and at least one component selected from the group consisting of surfactants, solid diluents and liquid diluents.

Preferred for better control of undesired vegetation (e.g., lower use rate such as from synergism, broader spectrum of weeds controlled, or enhanced crop safety) or for preventing the development of resistant weeds are mixtures of a compound of this invention with a herbicide selected from the group 2,4-D, acetochlor, alachlor, atrazine, bromoxynil, bentazon, bicyclopyrone, carfentrazone-ethyl, cloransulam-methyl, dicamba, dimethenamid-p, florasulam, flufenacet, flumioxazin, flupyrsulfuron-methyl, fluroxypyr-meptyl, glyphosate, halauxifen-methyl, isoxaflutole, MCPA, mesotrione, metolachlor, metsulfuron-methyl, nicosulfuron, pyrasulfotole, pyroxasulfone, pyroxsulam, rimsulfuron, saflufenacil, tembotrione, thifensulfuron-methyl, topramazone and tribenuron.

Table A1 lists specific combinations of a Component (a) with Component (b) illustrative of the mixtures, compositions and methods of the present invention. Compound 4 in the Component (a) column is identified in Index Table A. The second column of Table A1 lists the specific Component (b) compound (e.g., “2,4-D” in the first line). The third, fourth and fifth columns of Table A1 lists ranges of weight ratios for rates at which the Component (a) compound is typically applied to a field-grown crop relative to Component (b) (i.e. (a):(b)). Thus, for example, the first line of Table A1 specifically discloses the combination of Component (a) (i.e. Compound 4 in Index Table A) with 2,4-D is typically applied in a weight ratio between 1:192-6:1. The remaining lines of Table A1 are to be construed similarly.

TABLE A1 Component (a) Typical More Typical Most Typical (Compound #) Component (b) Weight Ratio Weight Ratio Weight Ratio 4 2,4-D 1:192-6:1 1:64-2:1 1:24-1:3 4 Acetochlor 1:768-2:1 1:256-1:2   1:96-1:11 4 Acifluorfen  1:96-12:1 1:32-4:1 1:12-1:2 4 Aclonifen 1:857-2:1 1:285-1:3  1:107-1:12 4 Alachlor 1:768-2:1 1:256-1:2   1:96-1:11 4 Ametryn 1:384-3:1 1:128-1:1  1:48-1:6 4 Amicarbazone 1:192-6:1 1:64-2:1 1:24-1:3 4 Amidosulfuron   1:6-168:1  1:2-56:1  1:1-11:1 4 Aminocyclopyrachlor  1:48-24:1 1:16-8:1  1:6-2:1 4 Aminopyralid  1:20-56:1  1:6-19:1  1:2-4:1 4 Amitrole 1:768-2:1 1:256-1:2   1:96-1:11 4 Anilofos  1:96-12:1 1:32-4:1 1:12-1:2 4 Asulam 1:960-2:1 1:320-1:3  1:120-1:14 4 Atrazine 1:192-6:1 1:64-2:1 1:24-1:3 4 Azimsulfuron   1:6-168:1  1:2-56:1  1:1-11:1 4 Beflubutamid 1:342-4:1 1:114-2:1  1:42-1:5 4 Benfuresate 1:617-2:1 1:205-1:2  1:77-1:9 4 Bensulfuron-methyl  1:25-45:1  1:8-15:1  1:3-3:1 4 Bentazone 1:192-6:1 1:64-2:1 1:24-1:3 4 Benzobicyclon  1:85-14:1 1:28-5:1 1:10-1:2 4 Benzofenap 1:257-5:1 1:85-2:1 1:32-1:4 4 Bicyclopyrone  1:42-27:1 1:14-9:1  1:5-2:1 4 Bifenox 1:257-5:1 1:85-2:1 1:32-1:4 4 Bispyribac-sodium   1:10-112:1  1:3-38:1  1:1-7:1 4 Bromacil 1:384-3:1 1:128-1:1  1:48-1:6 4 Bromobutide 1:384-3:1 1:128-1:1  1:48-1:6 4 Bromoxynil  1:96-12:1 1:32-4:1 1:12-1:2 4 Butachlor 1:768-2:1 1:256-1:2   1:96-1:11 4 Butafenacil  1:42-27:1 1:14-9:1  1:5-2:1 4 Butylate 1:1542-1:2  1:514-1:5  1:192-1:22 4 Carfenstrole 1:192-6:1 1:64-2:1 1:24-1:3 4 Carfentrazone-ethyl 1:128-9:1 1:42-3:1 1:16-1:2 4 Chlorimuron-ethyl   1:8-135:1  1:2-45:1  1:1-9:1 4 Chlorotoluron 1:768-2:1 1:256-1:2   1:96-1:11 4 Chlorsulfuron   1:6-168:1  1:2-56:1  1:1-11:1 4 Cincosulfuron  1:17-68:1  1:5-23:1  1:2-5:1 4 Cinidon-ethyl 1:384-3:1 1:128-1:1  1:48-1:6 4 Cinmethylin  1:34-34:1  1:11-12:1  1:4-3:1 4 Clacyfos  1:34-34:1  1:11-12:1  1:4-3:1 4 Clethodim  1:48-24:1 1:16-8:1  1:6-2:1 4 Clodinafop-propargyl  1:20-56:1  1:6-19:1  1:2-4:1 4 Clomazone 1:384-3:1 1:128-1:1  1:48-1:6 4 Clomeprop 1:171-7:1 1:57-3:1 1:21-1:3 4 Clopyralid 1:192-6:1 1:64-2:1 1:24-1:3 4 Cloransulam-methyl  1:12-96:1  1:4-32:1  1:1-6:1 4 Cumyluron 1:384-3:1 1:128-1:1  1:48-1:6 4 Cyanazine 1:384-3:1 1:128-1:1  1:48-1:6 4 Cyclopyrimorate  1:17-68:1  1:5-23:1  1:2-5:1 4 Cyclosulfamuron  1:17-68:1  1:5-23:1  1:2-5:1 4 Cycloxydim  1:96-12:1 1:32-4:1 1:12-1:2 4 Cyhalofop  1:25-45:1  1:8-15:1  1:3-3:1 4 Daimuron 1:192-6:1 1:64-2:1 1:24-1:3 4 Desmedipham 1:322-4:1 1:107-2:1  1:40-1:5 4 Dicamba 1:192-6:1 1:64-2:1 1:24-1:3 4 Dichlobenil 1:1371-1:2  1:457-1:4  1:171-1:20 4 Dichlorprop 1:925-2:1 1:308-1:3  1:115-1:13 4 Diclofop-methyl 1:384-3:1 1:128-1:1  1:48-1:6 4 Diclosulam   1:10-112:1  1:3-38:1  1:1-7:1 4 Difenzoquat 1:288-4:1 1:96-2:1 1:36-1:4 4 Diflufenican 1:857-2:1 1:285-1:3  1:107-1:12 4 Diflufenzopyr  1:12-96:1  1:4-32:1  1:1-6:1 4 Dimethachlor 1:768-2:1 1:256-1:2   1:96-1:11 4 Dimethametryn 1:192-6:1 1:64-2:1 1:24-1:3 4 Dimethenamid-P 1:384-3:1 1:128-1:1  1:48-1:6 4 Dithiopyr 1:192-6:1 1:64-2:1 1:24-1:3 4 Diuron 1:384-3:1 1:128-1:1  1:48-1:6 4 EPTC 1:768-2:1 1:256-1:2   1:96-1:11 4 Esprocarb 1:1371-1:2  1:457-1:4  1:171-1:20 4 Ethalfluralin 1:384-3:1 1:128-1:1  1:48-1:6 4 Ethametsulfuron-methyl  1:17-68:1  1:5-23:1  1:2-5:1 4 Ethoxyfen   1:8-135:1  1:2-45:1  1:1-9:1 4 Ethoxysulfuron  1:20-56:1  1:6-19:1  1:2-4:1 4 Etobenzanid 1:257-5:1 1:85-2:1 1:32-1:4 4 Fenoxaprop-ethyl  1:120-10:1 1:40-4:1 1:15-1:2 4 Fenoxasulfone  1:85-14:1 1:28-5:1 1:10-1:2 4 Fenquinotrione  1:17-68:1  1:5-23:1  1:2-5:1 4 Fentrazamide  1:17-68:1  1:5-23:1  1:2-5:1 4 Flazasulfuron  1:17-68:1  1:5-23:1  1:2-5:1 4 Florasulam   1:2-420:1   1:1-140:1  2:1-27:1 4 Fluazifop-butyl 1:192-6:1 1:64-2:1 1:24-1:3 4 Flucarbazone   1:8-135:1  1:2-45:1  1:1-9:1 4 Flucetosulfuron   1:8-135:1  1:2-45:1  1:1-9:1 4 Flufenacet 1:257-5:1 1:85-2:1 1:32-1:4 4 Flumetsulam  1:24-48:1  1:8-16:1  1:3-3:1 4 Flumiclorac-pentyl   1:10-112:1  1:3-38:1  1:1-7:1 4 Flumioxazin  1:25-45:1  1:8-15:1  1:3-3:1 4 Fluometuron 1:384-3:1 1:128-1:1  1:48-1:6 4 Flupyrsulfuron-methyl   1:3-336:1   1:1-112:1  2:1-21:1 4 Fluridone 1:384-3:1 1:128-1:1  1:48-1:6 4 Fluroxypyr  1:96-12:1 1:32-4:1 1:12-1:2 4 Flurtamone 1:857-2:1 1:285-1:3  1:107-1:12 4 Fluthiacet-methyl  1:48-42:1  1:16-14:1  1:3-3:1 4 Fomesafen  1:96-12:1 1:32-4:1 1:12-1:2 4 Foramsulfuron  1:13-84:1  1:4-28:1  1:1-6:1 4 Glufosinate 1:288-4:1 1:96-2:1 1:36-1:4 4 Glyphosate 1:288-4:1 1:96-2:1 1:36-1:4 4 Halosulfuron-methyl  1:17-68:1  1:5-23:1  1:2-5:1 4 Halauxifen  1:20-56:1  1:6-19:1  1:2-4:1 4 Halauxifen-methyl  1:20-56:1  1:6-19:1  1:2-4:1 4 Haloxyfop-methyl  1:34-34:1  1:11-12:1  1:4-3:1 4 Hexazinone 1:192-6:1 1:64-2:1 1:24-1:3 4 Hydantocidin 1:1100-16:1 1:385-8:1  1:144-4:1  4 Imazamox  1:13-84:1  1:4-28:1  1:1-6:1 4 Imazapic  1:20-56:1  1:6-19:1  1:2-4:1 4 Imazapyr  1:85-14:1 1:28-5:1 1:10-1:2 4 Imazaquin  1:34-34:1  1:11-12:1  1:4-3:1 4 Imazethabenz-methyl 1:171-7:1 1:57-3:1 1:21-1:3 4 Imazethapyr  1:24-48:1  1:8-16:1  1:3-3:1 4 Imazosulfuron  1:27-42:1  1:9-14:1  1:3-3:1 4 Indanofan 1:342-4:1 1:114-2:1  1:42-1:5 4 Indaziflam  1:25-45:1  1:8-15:1  1:3-3:1 4 lodosulfuron-methyl   1:3-336:1   1:1-112:1  2:1-21:1 4 Ioxynil 1:192-6:1 1:64-2:1 1:24-1:3 4 Ipfencarbazone  1:85-14:1 1:28-5:1 1:10-1:2 4 Isoproturon 1:384-3:1 1:128-1:1  1:48-1:6 4 Isoxaben 1:288-4:1 1:96-2:1 1:36-1:4 4 Isoxaflutole  1:60-20:1 1:20-7:1  1:7-2:1 4 Lactofen  1:42-27:1 1:14-9:1  1:5-2:1 4 Lenacil 1:384-3:1 1:128-1:1  1:48-1:6 4 Linuron 1:384-3:1 1:128-1:1  1:48-1:6 4 MCPA 1:192-6:1 1:64-2:1 1:24-1:3 4 MCPB 1:288-4:1 1:96-2:1 1:36-1:4 4 Mecoprop 1:768-2:1 1:256-1:2   1:96-1:11 4 Mefenacet 1:384-3:1 1:128-1:1  1:48-1:6 4 Mefluidide 1:192-6:1 1:64-2:1 1:24-1:3 4 Mesosulfuron-methyl   1:5-224:1  1:1-75:1  1:1-14:1 4 Mesotrione  1:42-27:1 1:14-9:1  1:5-2:1 4 Metamifop  1:42-27:1 1:14-9:1  1:5-2:1 4 Metazachlor 1:384-3:1 1:128-1:1  1:48-1:6 4 Metazosulfuron  1:25-45:1  1:8-15:1  1:3-3:1 4 Methabenzthiazuron 1:768-2:1 1:256-1:2   1:96-1:11 4 Metolachlor 1:768-2:1 1:256-1:2   1:96-1:11 4 Metosulam   1:8-135:1  1:2-45:1  1:1-9:1 4 Metribuzin 1:192-6:1 1:64-2:1 1:24-1:3 4 Metsulfuron-methyl   1:2-560:1   1:1-187:1  3:1-35:1 4 Molinate 1:1028-2:1  1:342-1:3  1:128-1:15 4 Napropamide 1:384-3:1 1:128-1:1  1:48-1:6 4 Napropamide-M 1:192-6:1 1:64-2:1 1:24-1:3 4 Naptalam 1:192-6:1 1:64-2:1 1:24-1:3 4 Nicosulfuron  1:12-96:1  1:4-32:1  1:1-6:1 4 Norflurazon 1:1152-1:1  1:384-1:3  1:144-1:16 4 Orbencarb 1:1371-1:2  1:457-1:4  1:171-1:20 4 Orthosulfamuron  1:20-56:1  1:6-19:1  1:2-4:1 4 Oryzalin 1:514-3:1 1:171-1:2  1:64-1:8 4 Oxadiargyl 1:384-3:1 1:128-1:1  1:48-1:6 4 Oxadiazon 1:548-3:1 1:182-1:2  1:68-1:8 4 Oxasulfuron  1:27-42:1  1:9-14:1  1:3-3:1 4 Oxaziclomefone  1:42-27:1 1:14-9:1  1:5-2:1 4 Oxyfluorfen 1:384-3:1 1:128-1:1  1:48-1:6 4 Paraquat 1:192-6:1 1:64-2:1 1:24-1:3 4 Pendimethalin 1:384-3:1 1:128-1:1  1:48-1:6 4 Penoxsulam   1:10-112:1  1:3-38:1  1:1-7:1 4 Penthoxamid 1:384-3:1 1:128-1:1  1:48-1:6 4 Pentoxazone  1:102-12:1 1:34-4:1 1:12-1:2 4 Phenmedipham  1:102-12:1 1:34-4:1 1:12-1:2 4 Picloram  1:96-12:1 1:32-4:1 1:12-1:2 4 Picolinafen  1:34-34:1  1:11-12:1  1:4-3:1 4 Pinoxaden  1:25-45:1  1:8-15:1  1:3-3:1 4 Pretilachlor 1:192-6:1 1:64-2:1 1:24-1:3 4 Primisulfuron-methyl   1:8-135:1  1:2-45:1  1:1-9:1 4 Prodiamine 1:384-3:1 1:128-1:1  1:48-1:6 4 Profoxydim  1:42-27:1 1:14-9:1  1:5-2:1 4 Prometryn 1:384-3:1 1:128-1:1  1:48-1:6 4 Propachlor 1:1152-1:1  1:384-1:3  1:144-1:16 4 Propanil 1:384-3:1 1:128-1:1  1:48-1:6 4 Propaquizafop  1:48-24:1 1:16-8:1  1:6-2:1 4 Propoxycarbazone  1:17-68:1  1:5-23:1  1:2-5:1 4 Propyrisulfuron  1:17-68:1  1:5-23:1  1:2-5:1 4 Propyzamide 1:384-3:1 1:128-1:1  1:48-1:6 4 Prosulfocarb 1:1200-1:2  1:400-1:4  1:150-1:17 4 Prosulfuron   1:6-168:1  1:2-56:1  1:1-11:1 4 Pyraclonil  1:42-27:1 1:14-9:1  1:5-2:1 4 Pyraflufen-ethyl   1:5-224:1  1:1-75:1  1:1-14:1 4 Pyrasulfotole  1:13-84:1  1:4-28:1  1:1-6:1 4 Pyrazolynate 1:857-2:1 1:285-1:3  1:107-1:12 4 Pyrazosulfuron-ethyl   1:10-112:1  1:3-38:1  1:1-7:1 4 Pyrazoxyfen   1:5-224:1  1:1-75:1  1:1-14:1 4 Pyribenzoxim   1:10-112:1  1:3-38:1  1:1-7:1 4 Pyributicarb 1:384-3:1 1:128-1:1  1:48-1:6 4 Pyridate 1:288-4:1 1:96-2:1 1:36-1:4 4 Pyriftalid   1:10-112:1  1:3-38:1  1:1-7:1 4 Pyriminobac-methyl  1:20-56:1  1:6-19:1  1:2-4:1 4 Pyrimisulfan  1:17-68:1  1:5-23:1  1:2-5:1 4 Pyrithiobac  1:24-48:1  1:8-16:1  1:3-3:1 4 Pyroxasulfone  1:85-14:1 1:28-5:1 1:10-1:2 4 Pyroxsulam   1:5-224:1  1:1-75:1  1:1-14:1 4 Quinclorac 1:192-6:1 1:64-2:1 1:24-1:3 4 Quizalofop-ethyl  1:42-27:1 1:14-9:1  1:5-2:1 4 Rimsulfuron  1:13-84:1  1:4-28:1  1:1-6:1 4 Saflufenacil  1:25-45:1  1:8-15:1  1:3-3:1 4 Sethoxydim  1:96-12:1 1:32-4:1 1:12-1:2 4 Simazine 1:384-3:1 1:128-1:1  1:48-1:6 4 Sulcotrione  1:120-10:1 1:40-4:1 1:15-1:2 4 Sulfentrazone 1:147-8:1 1:49-3:1 1:18-1:3 4 Sulfometuron-methyl  1:34-34:1  1:11-12:1  1:4-3:1 4 Sulfosulfuron   1:8-135:1  1:2-45:1  1:1-9:1 4 Tebuthiuron 1:384-3:1 1:128-1:1  1:48-1:6 4 Tefuryltrione  1:42-27:1 1:14-9:1  1:5-2:1 4 Tembotrione  1:31-37:1  1:10-13:1  1:3-3:1 4 Tepraloxydim  1:25-45:1  1:8-15:1  1:3-3:1 4 Terbacil 1:288-4:1 1:96-2:1 1:36-1:4 4 Terbuthylazine 1:857-2:1 1:285-1:3  1:107-1:12 4 Terbutryn 1:192-6:1 1:64-2:1 1:24-1:3 4 Thenylchlor  1:85-14:1 1:28-5:1 1:10-1:2 4 Thiazopyr 1:384-3:1 1:128-1:1  1:48-1:6 4 Thiencarbazone   1:3-336:1   1:1-112:1  2:1-21:1 4 Thifensulfuron-methyl   1:5-224:1  1:1-75:1  1:1-14:1 4 Tiafenacil  1:17-68:1  1:5-23:1  1:2-5:1 4 Thiobencarb 1:768-2:1 1:256-1:2   1:96-1:11 4 Tolpyralate  1:31-37:1  1:10-13:1  1:3-3:1 4 Topramzone   1:6-168:1  1:2-56:1  1:1-11:1 4 Tralkoxydim  1:68-17:1 1:22-6:1  1:8-2:1 4 Triafamone   1:2-420:1   1:1-140:1  2:1-27:1 4 Triallate 1:768-2:1 1:256-1:2   1:96-1:11 4 Triasulfuron   1:5-224:1  1:1-75:1  1:1-14:1 4 Triaziflam 1:171-7:1 1:57-3:1 1:21-1:3 4 Tribenuron-methyl   1:3-336:1   1:1-112:1  2:1-21:1 4 Triclopyr 1:192-6:1 1:64-2:1 1:24-1:3 4 Trifloxysulfuron   1:2-420:1   1:1-140:1  2:1-27:1 4 Trifludimoxazin  1:25-45:1  1:8-15:1  1:3-3:1 4 Trifluralin 1:288-4:1 1:96-2:1 1:36-1:4 4 Triflusulfuron-methyl  1:17-68:1  1:5-23:1  1:2-5:1 4 Tritosulfuron  1:13-84:1  1:4-28:1  1:1-6:1

Table A2 is constructed the same as Table A1 above except that entries below the “Component (a)” column heading are replaced with the respective Component (a) Column Entry shown below. Compound 5 in the Component (a) column is identified in Index Table A. Thus, for example, in Table A2 the entries below the “Component (a)” column heading all recite “Compound 5” (i.e. Compound 5 identified in Index Table A), and the first line below the column headings in Table A2 specifically discloses a mixture of Compound 5 with 2,4-D. Tables A3 through A78 are constructed similarly.

Table Number Component (a) Column Entries A2 Compound 5 A3 Compound 8 A4 Compound 10 A5 Compound 13 A6 Compound 18 A7 Compound 23 A8 Compound 35 A9 Compound 1 A10 Compound 2 A11 Compound 3 A12 Compound 4 A13 Compound 6 A14 Compound 7 A15 Compound 9 A16 Compound 11 A17 Compound 12 A18 Compound 14 A19 Compound 15 A20 Compound 16 A21 Compound 17 A22 Compound 19 A23 Compound 20 A24 Compound 21 A25 Compound 22 A26 Compound 24 A27 Compound 25 A28 Compound 26 A29 Compound 28 A30 Compound 29 A31 Compound 30 A32 Compound 31 A33 Compound 32 A34 Compound 33 A35 Compound 34 A36 Compound 36 A37 Compound 37 A38 Compound 38 A39 Compound 39 A40 Compound 40 A41 Compound 41 A42 Compound 42 A43 Compound 43 A44 Compound 44 A45 Compound 45 A46 Compound 46 A47 Compound 47 A48 Compound 48 A49 Compound 49 A50 Compound 50 A51 Compound 51 A52 Compound 52 A53 Compound 53 A54 Compound 54 A55 Compound 55 A56 Compound 56 A57 Compound 57 A58 Compound 58 A59 Compound 59 A60 Compound 60 A61 Compound 61 A62 Compound 62 A63 Compound 63 A64 Compound 64 A65 Compound 65 A66 Compound 66 A67 Compound 67 A68 Compound 68 A69 Compound 69 A70 Compound 70 A71 Compound 71 A72 Compound 72 A73 Compound 73 A74 Compound 74 A75 Compound 75 A76 Compound 76 A77 Compound 77 A78 Compound 78

The compounds of the present invention are useful for the control of weed species that are resistant to herbicides with the AHAS-inhibitor or (b2) [chemical compounds that inhibits acetohydroxy acid synthase (AHAS), also known as acetolactate synthase (ALS)] mode of action.

The following Tests demonstrate the control efficacy of the compounds of this invention against specific weeds. The weed control afforded by the compounds is not limited, however, to these species. See Index Table A for compound descriptions. The following abbreviations are used in the Index Table which follow: t is tertiary, s is secondary, n is normal, i is iso, c is cyclo, Me is methyl, Et is ethyl, Pr is propyl, i-Pr is isopropyl, Bu is butyl, c-Pr is cyclopropyl, t-Bu is tert-butyl, Ph is phenyl, OMe is methoxy, OEt is ethoxy, SMe is methylthio and —CN is cyano. The abbreviation “Cmpd. No.” stands for “Compound Number”. The abbreviation “Ex.” stands for “Example” and is followed by a number indicating in which example the compound is prepared. Mass spectra are reported with an estimated precision within ±0.5 Da as the molecular weight of the highest isotopic abundance parent ion (M+1) formed by addition of H⁺ (molecular weight of 1) to the molecule. The presence of molecular ions containing one or more higher atomic weight isotopes of lower abundance (e.g., ³⁷Cl, ⁸¹Br) is not reported. The alternate molecular ion peaks (e.g., M+2 or M+4) that occur with compounds containing multiple halogens are not reported. The reported M+1 peaks were observed by mass spectrometry using atmospheric pressure chemical ionization (AP⁺) or electrospray ionization (ESI).

TABLE A INDEX

Cmpd. M.S.(AP+) No. A R¹ R² R³ or m.p.  1 CH₂CF₃ Cl CN H 330  2 CH₂(2-Cl—Ph) Cl CN H 372  3 CH₂(4-Cl—Ph) Cl CN H 372  4 CH₂CH₂CH₂CF₃ F CN H 70-74  5 CH₂CH₂CH₂CF₃ Cl CN H 51-54  6 CH₂(5-Cl-2-pyridinyl) Cl CN H 373  7 E—CH₂CH═CHCl Cl CN H 322  8 E—CH₂CH═CH(CF₃) Cl CN H 102-106  9 E—CH₂CH═CHCl Cl F H 315 10 CH₂CF₂CF₃ Cl CN H 381 11 CH₂CH₂CH₂CH(CH₃)₂ Cl Br H 385 12 CH₂CH₂CH(CH₃)₂ Cl Br H * 13 (Ex. 2) CH₂CH₂CH₂CH₃ Cl Br H 357 14 CH₂CF₂CHF₂ Cl CN H 362 15 CH₂CH₂CH₂F Cl CN H 308 16 CH₂CHF₂ Cl CN H * 17 CH₂CHF₂ Cl Br H 365 18 CH₂CF₂CHF₂ Cl Br H 415 19 CH₂(4-CF₃—Ph) Cl Br H 461 20 CH₂(4-CF₃—Ph) Cl CN H 406 21 CH₂(3-Cl—Ph) Cl CN H 372 22 CH₂CH₂CH₂CN Cl CN H 315 23 CH₂CH₂CF₃ Cl CN H 344 24 CH₂CH₂CH₂CN Cl F H 76-79 25 E—CH₂CH═CH(CF₃) Cl F H 349 26 CH₂CH₂CH₂F Cl F H 301 27 CH₂CH₂CH₂CF₃ Cl F H 351 28 CH₂CF₃ Cl F H 323 29 CH₂CH₂CF₃ Cl F H 337 30 CH₂CH₂CH₂F F CN H 51-54 31 CH₂CH₂CH₂CF₃ Cl Br H 411 32 CH₂CH₂CH₂CH₂CF₃ Cl CN H 372 33 CH₂CH₂CH₂CH₂CF₃ Cl Br H 425 34 CH₂CH(CH₃)CH₂CF₃ Cl CN H 372 35 (Ex. 1) CH₂CH₂CH₂CH₃ Cl CN H 302 36 E—CH₂CH═CHCl F CN H 52-54 37 CH₂CH₂CH₂CN F CN H 50-53 38 CH₂CH₂CF═CF₂ Cl Br H * 39 E—CH₂CH═CH(CF₃) F CN H 68-72 40 CH₂CH₂CF₃ F CN H 328 41 CH₂CF₃ F CN H 58-63 42 CH₂CF₃ Cl Cl H 339 43 CH₂CH₂CF₃ Cl Cl H 353 44 CH₂CH₂CH₂F Cl Cl H 317 45 CH₂CH₂CH₂CN Cl Cl H 65-68 46 CH₂CH₂CH₂CF₃ Cl Cl H 50-53 47 E—CH₂CH═CHCF₃ Cl Cl H 49-52 48 E—CH₂CH═CHCl Cl Cl H 332 49 CH₂CH₂CH₂CF₂CF₃ Cl Br H * 50 CH₂CH₂CH₃ Cl CN H * 51 CH₂CH₂CH₂CH₂CH₃ Cl CN H * 52 (Ex. 3) CH₂CF₂CF₂CF₃ Cl Br H 483** 53 CH₂CF₂CF₂CF₂CHF₂ Cl Br H * 54 CH₂CH₂CH₂CF₃ Cl CF₃ H 401 55 CH₂CH₂CH₂CF₃ Cl CH₃ H 40-42 56 CH₂(C═O)CH₂CH₂CF₃ Cl Br H * 57 CH₂CH₂CH₂F Cl CH₃ H 297 58 E—CH₂CH═CHCF₃ Cl CH₃ H 88-92 59 E—CH₂CH═CHCl Cl CH₃ H 311 60 CH₂CH₂CH₂CF₃ Cl I H 459 61 E—CH₂CH═CHCF₃ Cl I H 74-78 62 CH₂(C═O)CH₂CH₂CF₃ Cl CN H 164-168 63 CH₂CF₃ Cl CH₃ H 319 64 CH₂CH₂CF₃ Cl CH₃ H 333 65 CH₂CF₃ Cl I H 87-90 66 CH₂CH₂CH₂F Cl I H 45-48 67 CH₂CH₂CH₂CN Cl I H 44-18 68 E—CH₂CH═CHCl Cl I H 423 69 CH₂CH₂CF₃ Cl I H 58-62 70 CH₂CH₂CH₂CN Cl CH₃ H 304 71 CH₂CH₂CH₂F Cl C═CH H 307 72 CH₂CH₂CH₂CF₃ Cl CN H 357 73 CH₂(C═O)CF₂CF₃ Cl Br H * 74 CH₂(C═O)CF₂CF₃ Cl CN H * 75 CH₂(C═O)CH₂CH₃ Cl CN H 318*  76 CH₂(C═O)CH₂CH₃ Cl Br H * 77 4,4-difluorocyclohexan-1-yl Cl CN H * 78 tetrahydrofuran-2-yl Cl CN H * *See Index Table B for ¹H NMR data. **ES⁺ E indicates the E isomer as the predominant double bond configuration of.?

INDEX TABLE B Cmpd ¹H NMR (CDCl₃ solution unless indicated otherwise) 12 δ 8.48 (s, 2H), 7.48 (d, 1H), 7.17 (d, 1H), 7.02 (t, 1H), 4.00 (t, 2H), 1.63 (m, 1H), 1.51 (m, 2H), 0.86 (s, 3H), 0.85 (s, 3H). 16 δ 8.50 (s, 2H), 7.54 (d, 1H), 7.46 (d, 1H), 7.29 (t, 1H), 6.01 (t, 1H), 4.35 (m, 2H). 38 δ 8.48 (s, 2H), 7.48 (d, 1H), 7.18 (d, 1H), 7.08 (t, 1H), 4.03 (m, 2H), 2.61 (m, 2H). 49 (500 MHz) δ 8.48 (s, 2H), 7.49 (d, 1H), 7.19 (d, 1H), 7.08 (t, 1H), 4.07 (t, 2H), 2.09 (m, 2H), 1.91 (m, 2H). 50 (500 MHz) δ 8.49 (s, 2H), 7.50 (d, 1H), 7.41 (d, 1H), 7.20 (t, 1H), 4.11 (t, 2H), 1.64 (m, 2H), 0.88 (t, 3H). 51 (500 MHz) δ 8.49 (s, 2H), 7.50 (d, 1H), 7.41 (d, 1H), 7.20 (t, 1H), 4.15 (t, 2H), 4.61 (m, 2H), 4.23 (m, 4H), 1.85 (t, 3H). 53 (500 MHz) δ 8.48 (s, 2H), 7.53 (d, 1H), 7.21 (d, 1H), 7.12 (t, 1H), 6.02 (t, 1H), 4.49 (m, 2H). 56 (400 MHz) δ 8.48 (s, 2H), 7.51 (d, 1H), 7.18 (d, 1H), 7.11 (t, 1H), 4.55 (s, 2H), 2.82 (q, 2H), 1.54 (m, 2H). 73 (400 MHz, dmso-d₆) δ 8.77 (s, 2H), 7.57 (d, 1H), 7.31 (d, 1H), 7.17 (t, 1H), 4.03 (s, 2H). 74 (400 MHz) δ 8.55 (s, 2H), 7.55 (d, 1H), 7.52 (d, 1H), 7.31 (t, 1H), 4.42 (s, 2H). 75 (400 MHz) δ 8.48 (s, 2H), 7.53 (d, 1H), 7.43 (d, 1H), 7.23 (t, 1H), 4.75 (s, 2H), 2.57 (q, 2H), 1.06 (t, 2H). 76 (400 MHz) δ 8.47 (s, 2H), 7.5 (d, 1H), 7.18 (d, 1H), 7.10 (t, 1H), 4.5 (s, 2H), 2.5 (q, 2H), 1.05 (t, 3H). 77 (500 MHz) δ 8.48 (s, 2H), 7.51 (m, 1H), 7.41 (m, 1H), 7.22 (m, 1H), 4.58 (s, 1H), 2.17-1.84 (m, 8H). 78 (500 MHz) δ 8.48 (s, 2H), 7.53 (m, 1H), 7.44 (m, 1H), 7.24 (m, 1H), 5.15 (s, 1H), 3.86 (m, 4H), 2.15 (m, 1H), 2.02 (m, 1H). ¹H NMR data are in ppm downfield from tetramethylsilane. Couplings are designated by (s)-singlet, (d)-doublet, (t)-triplet, (m)-multiplet.

BIOLOGICAL EXAMPLES OF THE INVENTION

Test A

Seeds of plant species selected from barnyardgrass (Echinochloa crus-galli), kochia (Kochia scoparia), ragweed (common ragweed, Ambrosia elatior), ryegrass, Italian (Italian ryegrass, Lolium multiflorum), foxtail, giant (giant foxtail, Setaria faberii), and pigweed (Amaranthus retroflexus), were planted into a blend of loam soil and sand and treated preemergence with a directed soil spray using test chemicals formulated in a non-phytotoxic solvent mixture which included a surfactant.

At the same time, plants selected from these weed species and also wheat (Triticum aestivum), corn (Zea mays), blackgrass (Alopecurus myosuroides), and galium (catchweed bedstraw, Galium aparine), were planted in pots containing the same blend of loam soil and sand and treated with postemergence applications of test chemicals formulated in the same manner. Plants ranged in height from 2 to 10 cm and were in the one- to two-leaf stage for the postemergence treatment. Treated plants and untreated controls were maintained in a greenhouse for approximately 10 days, after which time all treated plants were compared to untreated controls and visually evaluated for injury. Plant response ratings, summarized in Table A, are based on a 0 to 100 scale where 0 is no effect and 100 is complete control. A dash (—) response means no test result.

TABLE A 500 g ai/ha Compounds Postemergence 2 3 9 10 11 12 13 14 16 17 18 19 20 21 Barnyardgrass 10 50 80 100 90 100 100 100 90 90 100 20 30 20 Blackgrass 0 50 70 100 40 60 100 90 90 90 80 10 20 20 Corn 30 20 30 100 30 30 90 50 70 50 30 30 20 20 Foxtail, Giant 10 70 80 100 60 100 100 100 100 100 100 20 30 40 Galium 50 90 90 100 100 100 100 100 90 80 100 30 80 70 Kochia 40 90 100 100 90 100 100 100 100 100 100 50 100 70 Pigweed 10 100 100 100 100 100 100 100 100 100 100 100 90 60 Ragweed 10 60 0 50 0 20 10 20 60 40 20 20 30 20 Ryegrass, Italian 0 30 10 90 20 30 90 50 80 70 60 0 20 0 Wheat 0 10 10 90 20 20 40 40 20 20 20 20 10 10 500 g ai/ha Compounds Postemergence 24 25 26 27 28 29 34 35 52 53 Barnyardgrass 50 90 60 80 20 70 50 100 80 100 Blackgrass 20 80 50 60 20 50 60 90 20 60 Corn 10 20 10 10 10 10 40 70 30 30 Foxtail, Giant 30 80 70 80 20 80 90 90 80 100 Galium 80 100 50 90 20 50 90 100 90 100 Kochia 100 100 90 100 10 80 100 100 90 100 Pigweed 70 70 90 60 70 100 100 100 100 100 Ragweed 50 0 20 10 0 10 10 20 30 80 Ryegrass, Italian 0 70 0 30 0 20 20 80 40 70 Wheat 0 20 0 10 0 20 20 40 20 30 125 g ai/ha Compounds Postemergence 1 2 3 4 5 6 7 8 9 10 11 12 13 14 Barnyardgrass 30 0 50 90 100 10 90 60 20 90 10 10 90 80 Blackgrass 20 0 20 90 90 10 30 40 10 90 0 20 50 60 Corn 10 0 10 90 80 20 20 20 10 70 30 30 30 20 Foxtail, Giant 20 0 60 100 100 10 90 90 20 100 20 10 90 80 Galium 40 20 60 90 100 40 80 90 60 90 70 70 90 50 Kochia 80 30 70 100 100 60 100 100 70 100 20 90 100 100 Pigweed 90 0 100 100 100 80 90 100 60 100 60 70 100 100 Ragweed 10 0 60 20 30 0 10 10 0 0 0 10 0 10 Ryegrass, Italian 0 0 20 40 40 0 50 60 0 30 0 0 20 10 Wheat 0 0 0 20 40 0 10 10 0 30 0 0 20 20 125 g ai/ha Compounds Postemergence 15 16 17 18 19 20 21 22 23 24 25 26 27 28 Barnyardgrass 90 20 20 30 0 10 10 0 90 0 40 10 50 0 Blackgrass 10 10 10 20 0 0 0 0 70 0 20 0 30 0 Corn 10 20 20 20 10 10 10 20 90 0 10 0 0 0 Foxtail, Giant 30 30 40 40 0 10 10 10 90 0 30 10 20 0 Galium 50 30 30 80 0 30 20 50 90 20 50 70 30 0 Kochia 80 100 100 100 10 50 40 90 100 80 90 60 80 0 Pigweed 70 90 100 100 20 90 50 80 100 40 50 60 50 30 Ragweed 20 10 0 0 10 20 10 10 30 10 0 0 0 0 Ryegrass, Italian 10 0 0 0 0 0 0 0 40 0 0 0 0 0 Wheat 0 0 0 0 0 10 0 20 70 0 0 0 0 0 125 g ai/ha Compounds Postemergence 29 30 31 32 33 34 35 36 37 38 39 40 41 42 Barnyardgrass 20 10 70 100 60 20 80 70 20 30 40 50 0 10 Blackgrass 0 0 40 50 40 20 70 50 10 10 60 30 10 10 Corn 0 0 20 20 20 20 20 20 20 20 50 20 10 10 Foxtail, Giant 20 0 50 80 60 40 90 50 10 40 90 80 0 10 Galium 20 0 90 100 90 70 90 50 60 50 60 60 20 20 Kochia 40 10 100 100 90 90 100 90 80 70 90 70 60 10 Pigweed 50 0 100 100 100 100 90 50 70 80 100 90 70 60 Ragweed 0 10 10 10 10 10 10 40 50 10 10 10 10 0 Ryegrass, Italian 0 40 50 30 20 0 40 20 0 10 50 10 10 0 Wheat 0 0 10 30 10 10 10 0 0 0 20 0 0 0 125 g ai/ha Compounds Postemergence 43 44 45 46 47 48 49 50 51 52 53 54 55 56 Barnyardgrass 30 10 10 30 40 50 0 20 30 10 40 20 20 20 Blackgrass 30 10 0 40 50 10 0 10 20 10 30 10 20 20 Corn 10 10 10 20 20 20 10 10 20 10 10 20 20 30 Foxtail, Giant 40 20 10 60 70 60 10 20 40 20 30 70 60 30 Galium 60 20 20 70 80 30 30 40 70 40 90 50 20 40 Kochia 80 70 50 80 90 100 30 80 70 70 100 50 20 60 Pigweed 90 70 50 90 90 80 60 70 40 80 100 80 30 100 Ragweed 0 0 10 10 10 10 20 10 10 20 40 10 0 0 Ryegrass, Italian 0 0 0 10 10 0 20 0 10 20 20 20 20 10 Wheat 0 0 0 0 0 10 0 0 0 0 10 10 0 20 125 g ai/ha Compounds Postemergence 57 58 59 60 61 62 63 64 65 66 67 68 69 70 Barnyardgrass 0 70 100 100 50 0 0 10 60 50 30 100 100 30 Blackgrass 0 30 50 50 0 0 0 10 30 30 30 60 80 0 Corn 10 10 10 30 30 0 0 10 20 30 20 30 70 20 Foxtail, Giant 10 70 50 80 30 0 0 10 50 30 30 80 100 0 Galium 0 30 30 100 50 0 0 0 50 90 50 60 100 20 Kochia 20 — — 90 90 0 0 20 100 100 100 100 100 30 Pigweed 20 30 70 90 90 0 0 30 100 100 100 100 100 40 Ragweed 0 0 0 30 0 0 0 0 0 0 10 20 40 20 Ryegrass, Italian 0 0 0 70 0 0 0 0 10 20 10 30 90 0 Wheat 0 0 0 20 0 0 0 0 0 0 0 0 30 0 125 g ai/ha Compounds Postemergence 71 72 73 74 75 76 Barnyardgrass 0 30 10 20 0 20 Blackgrass 0 20 20 0 0 10 Corn 0 20 10 20 10 10 Foxtail, Giant 0 40 10 40 0 40 Galium 0 60 40 30 20 20 Kochia 0 70 50 20 20 10 Pigweed 0 60 60 70 20 30 Ragweed 0 10 0 20 0 0 Ryegrass, Italian 0 10 0 0 0 0 Wheat 0 0 0 0 0 0 31 g ai/ha Compounds Postemergence 1 4 5 6 7 8 15 22 23 30 31 32 33 36 Barnyardgrass 0 20 70 0 10 20 60 0 50 0 20 60 10 0 Blackgrass 0 40 30 0 10 20 0 0 20 0 20 30 10 10 Corn 10 40 50 10 10 10 10 10 10 0 10 10 10 0 Foxtail, Giant 10 70 60 0 10 20 10 0 20 0 20 50 20 0 Galium 10 50 80 30 50 40 20 20 60 0 40 70 50 40 Kochia 60 90 100 10 90 80 50 80 90 0 90 100 50 80 Pigweed 60 100 100 20 60 90 60 30 100 0 80 100 80 50 Ragweed 10 0 10 0 0 0 0 0 0 0 0 10 0 20 Ryegrass, Italian 0 0 20 0 10 10 0 0 20 30 10 10 0 0 Wheat 0 20 20 0 0 0 0 0 20 0 0 20 0 0 31 g ai/ha Compounds Postemergence 37 38 39 40 41 42 43 44 45 46 47 48 49 50 Barnyardgrass 10 10 20 0 0 0 0 0 0 0 10 10 0 0 Blackgrass 0 0 10 10 0 0 0 0 0 0 10 0 0 0 Corn 0 10 20 10 0 0 10 0 0 10 10 10 10 10 Foxtail, Giant 0 10 20 10 0 0 10 0 0 20 20 20 0 0 Galium 40 10 20 20 10 0 20 10 10 30 50 10 10 10 Kochia 50 20 90 50 30 0 30 20 20 50 50 60 0 20 Pigweed 60 40 90 80 30 20 50 30 20 50 20 50 10 20 Ragweed 30 0 0 0 10 0 0 0 10 0 0 0 10 10 Ryegrass, Italian 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Wheat 0 0 0 0 0 0 0 0 0 0 0 0 0 0 31 g ai/ha Compounds Postemergence 51 54 55 56 57 58 59 60 61 62 63 64 65 66 Barnyardgrass 10 10 10 0 0 50 40 30 0 0 0 0 0 0 Blackgrass 0 0 0 0 0 0 0 30 0 0 0 0 0 10 Corn 10 10 0 10 0 0 0 30 10 0 0 0 10 0 Foxtail, Giant 10 10 20 0 0 20 20 30 0 0 0 0 10 10 Galium 40 20 0 10 0 0 90 70 20 0 0 0 30 40 Kochia 40 10 10 0 0 — — 90 40 0 0 10 80 90 Pigweed 10 20 10 40 10 10 40 90 80 0 0 20 70 90 Ragweed 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Ryegrass, Italian 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Wheat 0 0 0 0 0 0 0 0 0 0 0 0 0 0 31 g ai/ha Compounds Postemergence 67 68 69 70 71 72 73 74 75 76 Barnyardgrass 0 60 60 0 0 10 0 0 0 0 Blackgrass 0 20 30 0 0 0 0 0 0 0 Corn 10 20 20 0 0 10 0 0 0 0 Foxtail, Giant 10 30 40 0 0 10 0 0 0 10 Galium 30 50 60 0 0 20 10 0 10 10 Kochia 60 90 90 20 0 30 0 0 10 0 Pigweed 60 80 100 20 0 30 30 20 10 10 Ragweed 0 0 30 0 0 0 0 20 0 0 Ryegrass, Italian 0 0 0 0 0 0 0 0 0 0 Wheat 0 0 0 0 0 0 0 0 0 0 500 g ai/ha Compounds Preemergence 2 3 9 10 11 12 13 14 16 17 18 19 20 21 Barnyardgrass 10 90 100 100 90 100 100 100 100 100 100 60 30 10 Foxtail, Giant 70 100 100 100 100 100 100 100 100 100 100 90 100 100 Kochia 0 90 100 100 0 70 100 100 100 100 100 0 50 30 Pigweed 20 90 100 100 80 100 100 100 100 100 100 0 100 40 Ragweed 0 10 0 10 0 0 10 0 90 30 10 0 0 0 Ryegrass, Italian 0 30 20 100 30 40 90 70 40 70 100 20 20 10 500 g ai/ha Compounds Preemergence 24 25 26 27 28 29 34 35 52 53 Barnyardgrass 70 100 100 100 70 100 100 100 50 100 Foxtail, Giant 100 100 100 100 70 100 100 100 100 100 Kochia 100 100 100 100 20 100 100 100 40 90 Pigweed 100 100 100 100 100 100 100 100 100 100 Ragweed 70 20 20 20 0 20 10 30 0 20 Ryegrass, Italian 20 100 20 90 20 70 40 90 50 80 125 g ai/ha Compounds Preemergence 1 2 3 4 5 6 7 8 9 10 11 12 13 14 Barnyardgrass 80 0 50 100 100 0 100 100 40 100 20 70 100 90 Foxtail, Giant 100 10 90 100 100 20 100 100 100 100 90 90 100 100 Kochia 100 0 80 90 100 0 100 100 40 100 0 0 80 90 Pigweed 100 0 90 100 90 90 100 100 80 100 0 40 100 100 Ragweed 100 0 0 30 10 0 0 0 0 20 0 0 0 0 Ryegrass, Italian 10 0 20 60 60 0 10 30 0 40 0 0 10 10 125 g ai/ha Compounds Preemergence 15 16 17 18 19 20 21 22 23 24 25 26 27 28 Barnyardgrass 20 80 80 100 0 20 0 20 100 20 90 40 90 10 Foxtail, Giant 90 100 100 100 10 90 40 90 100 30 100 50 80 0 Kochia 100 100 90 30 0 0 0 90 100 60 30 10 70 0 Pigweed 100 100 100 100 0 30 10 100 100 90 100 90 90 0 Ragweed 0 60 0 0 0 0 0 30 90 0 0 0 0 0 Ryegrass, Italian 10 10 10 10 0 0 0 0 30 0 60 0 40 0 125 g ai/ha Compounds Preemergence 29 30 31 32 33 34 35 36 37 38 39 40 41 42 Barnyardgrass 70 20 60 100 50 70 100 80 20 70 100 80 40 10 Foxtail, Giant 70 30 100 100 100 100 100 90 50 100 100 90 80 10 Kochia 40 90 70 90 20 80 100 100 80 70 100 100 100 10 Pigweed 100 80 100 100 90 100 100 100 100 100 100 100 100 60 Ragweed 0 30 10 10 0 0 10 0 70 0 10 90 20 0 Ryegrass, Italian 10 20 40 30 20 10 30 0 0 10 20 10 10 0 125 g ai/ha Compounds Preemergence 43 44 45 46 47 48 49 50 51 52 53 54 55 56 Barnyardgrass 70 20 10 80 50 60 10 20 40 30 60 90 70 90 Foxtail, Giant 100 80 30 100 100 80 40 90 100 80 100 100 80 90 Kochia 90 40 30 80 80 80 0 100 40 0 20 30 60 50 Pigweed 100 100 70 100 60 60 0 100 50 70 80 100 50 80 Ragweed 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Ryegrass, Italian 10 0 0 10 10 10 0 0 0 10 20 80 10 0 125 g ai/ha Compounds Preemergence 57 58 59 60 61 62 63 64 65 66 67 68 69 70 Barnyardgrass 20 90 100 80 20 0 0 60 70 70 30 70 100 70 Foxtail, Giant 30 90 50 90 80 0 0 20 100 100 100 100 100 30 Kochia 20 0 100 40 0 0 0 0 90 60 80 30 100 20 Pigweed 60 100 100 100 70 0 0 100 100 100 100 100 100 50 Ragweed 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Ryegrass, Italian 0 0 0 90 0 0 0 0 10 10 20 20 50 0 125 g ai/ha Compounds Preemergence 71 72 73 74 75 76 Barnyardgrass 0 80 0 30 50 40 Foxtail, Giant 0 90 0 70 40 70 Kochia 0 10 0 0 60 0 Pigweed 0 60 50 80 100 80 Ragweed 0 0 0 0 0 0 Ryegrass, Italian 0 20 0 0 0 10 31 g ai/ha Compounds Preemergence 1 4 5 6 7 8 15 22 23 30 31 32 33 36 Barnyardgrass 10 60 80 0 20 30 0 0 70 0 10 30 10 30 Foxtail, Giant 60 100 100 0 60 100 30 0 90 10 40 100 60 30 Kochia 60 40 90 0 70 20 50 70 100 90 0 30 0 10 Pigweed 100 90 90 10 60 100 100 80 100 50 70 100 10 100 Ragweed 0 10 10 0 0 0 0 10 0 20 0 0 0 0 Ryegrass, Italian 0 10 20 0 0 0 0 0 0 0 0 10 0 0 31 g ai/ha Compounds Preemergence 37 38 39 40 41 42 43 44 45 46 47 48 49 50 Barnyardgrass 0 10 50 30 0 0 20 10 0 10 10 10 0 10 Foxtail, Giant 20 30 90 70 20 0 10 10 0 40 30 30 0 10 Kochia 30 0 60 90 50 0 0 0 0 0 0 0 0 20 Pigweed 100 0 100 100 100 0 40 10 20 0 0 0 0 20 Ragweed 30 0 0 10 0 0 0 0 0 0 0 0 0 0 Ryegrass, Italian 0 0 0 0 0 0 0 0 0 0 0 0 0 0 31 g ai/ha Compounds Preemergence 51 54 55 56 57 58 59 60 61 62 63 64 65 66 Barnyardgrass 10 20 10 0 0 40 30 20 0 0 0 10 — 20 Foxtail, Giant 40 50 10 0 0 40 10 90 0 0 0 0 30 50 Kochia 0 0 0 0 0 0 60 30 0 0 0 0 20 0 Pigweed 10 20 0 0 0 0 20 70 0 0 0 0 50 70 Ragweed 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Ryegrass, Italian 0 10 0 0 0 0 0 0 0 0 0 0 0 0 31 g ai/ha Compounds Preemergence 67 68 69 70 71 72 73 74 75 76 Barnyardgrass 0 70 90 0 0 10 0 0 0 20 Foxtail, Giant 60 70 90 0 0 10 0 0 0 10 Kochia 20 0 80 0 0 0 0 0 0 0 Pigweed 50 0 90 0 0 0 40 60 50 0 Ragweed 0 0 0 0 0 0 0 0 0 0 Ryegrass, Italian 0 0 10 0 0 0 0 0 0 0 Test B

Plant species in the flooded paddy test selected from rice (Oryza sativa), sedge, umbrella (small-flower umbrella sedge, Cyperus difformis), ducksalad (Heteranthera limosa), and barnyardgrass (Echinochloa crus-galli) were grown to the 2-leaf stage for testing. At time of treatment, test pots were flooded to 3 cm above the soil surface, treated by application of test compounds directly to the paddy water, and then maintained at that water depth for the duration of the test. Treated plants and controls were maintained in a greenhouse for 13 to 15 days, after which time all species were compared to controls and visually evaluated. Plant response ratings, summarized in Table B, are based on a scale of 0 to 100 where 0 is no effect and 100 is complete control. A dash (—) response means no test result.

TABLE B 250 g ai/ha Compounds Flood 2 3 4 5 6 8 9 10 11 12 13 14 16 17 Barnyardgrass 0 0 50 50 0 0 0 50 0 0 0 0 0 0 Ducksalad 0 0 90 90 0 75 80 70 0 0 50 0 30 85 Rice 0 0 30 40 0 0 0 20 0 0 20 0 0 0 Sedge, Umbrella 0 80 95 95 0 100 80 85 0 0 95 0 0 80 250 g ai/ha Compounds Flood 18 19 20 21 22 23 24 25 26 27 28 29 30 31 Barnyardgrass 0 0 0 0 0 50 0 0 0 0 0 0 0 25 Ducksalad 30 0 0 0 0 100 30 100 30 90 30 50 30 75 Rice 0 0 0 0 0 30 0 0 0 0 0 0 0 25 Sedge, Umbrella 0 0 0 0 0 100 0 75 0 70 0 0 40 100 250 g ai/ha Compounds Flood 32 33 34 35 38 39 40 42 43 44 45 46 47 48 Barnyardgrass 30 0 0 30 0 30 0 0 0 0 0 0 0 20 Ducksalad 90 30 40 65 75 65 75 70 100 70 20 98 85 70 Rice 40 0 20 0 0 15 0 0 50 0 0 0 0 20 Sedge, Umbrella 100 95 75 70 100 100 70 60 90 30 0 100 100 70 250 g ai/ha Compounds Flood 49 50 51 52 53 54 55 56 57 58 59 60 61 62 Barnyardgrass 0 30 0 0 0 40 40 0 0 0 20 20 20 0 Ducksalad 0 50 80 75 90 100 100 85 70 100 100 100 100 0 Rice 0 0 0 15 15 40 45 30 0 15 0 25 25 0 Sedge, Umbrella 0 60 95 90 80 100 95 75 30 100 90 95 95 0 250 g ai/ha Compounds Flood 63 64 65 66 67 68 69 70 71 72 73 74 75 76 Barnyardgrass 0 0 20 0 0 40 40 0 0 25 0 0 0 10 Ducksalad 100 85 100 100 100 100 100 70 0 100 0 0 30 90 Rice 0 20 0 20 10 10 15 0 0 0 0 0 0 10 Sedge, Umbrella 90 90 90 100 95 100 100 50 0 90 0 0 0 70 

What is claimed is:
 1. A compound selected from Formula 1, N-oxides and salts thereof,

wherein A is C₂-C₈ alkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl, C₂-C₈ haloalkyl, C₂-C₆ haloalkenyl, C₂-C₆ haloalkynyl, C₃-C₆ cycloalkyl, C₃-C₆ halocycloalkyl, C₄-C₈ alkylcycloalkyl, C₄-C₈ cycloalkylalkyl, C₂-C₆ alkoxyalkyl, C₂-C₆ haloalkoxyalkyl, C₂-C₆ alkoxyhaloalkyl, C₄-C₈ cycloalkoxyalkyl, C₂-C₆ cyanoalkyl, C₃-C₇ cyanoalkoxyalkyl, C₁-C₆ nitroalkyl, C₂-C₆ alkylthioalkyl, C₂-C₆ haloalkylthioalkyl, C₃-C₈ cycloalkylthioalkyl, C₂-C₆ alkylsulfinylalkyl, C₂-C₆ haloalkylsulfinylalkyl, C₂-C₆ alkylsulfonylalkyl, C₂-C₆ haloalkylsulfonylalkyl, C₂-C₆ alkylcarbonyl, C₂-C₆ haloalkylcarbonyl, C₂-C₆ alkylcarbonylalkyl, C₂-C₆ haloalkylcarbonylalkyl, C₂-C₆ alkoxycarbonylalkyl, C₂-C₆ haloalkoxycarbonylalkyl or C₂-C₆ alkoxyalkylcarbonyl; or G; or C₁-C₄ alkyl substituted with Q; R¹ is halogen or C₁-C₄ alkyl; R² is halogen, cyano, C₁-C₄ alkyl or C₁-C₄ haloalkyl; R³ is H; G is a 3- to 7-membered nonaromatic heterocyclic ring containing ring members selected from carbon, up to 4 heteroatoms selected from up to 2 O, up to 2 S and up to 4 N, and up to 3 ring members selected from C(═O), C(═S) and S(═O)_(a)(═NR⁶)_(b) and substituted with up to 3 substituents independently selected from halogen, cyano, C₁-C₄ alkyl, C₁-C₄ haloalkyl, C₁-C₄ alkoxy or C₁-C₄ haloalkoxy; Q is a phenyl ring optionally substituted with up to 5 substituents independently selected from R⁸; or a 5- or 6-membered heteroaromatic ring containing ring members selected from carbon atoms and up to 4 heteroatoms independently selected from up to 2 O, up to 2 S and up to 4 N atoms and optionally substituted with up to 3 substituents independently selected from R^(9a) on carbon atom ring members and R^(9b) on nitrogen atom ring members; each R⁶ is independently H or C₁-C₄ alkyl; each R⁸ is independently halogen, cyano, C₁-C₄ alkyl, C₁-C₄ haloalkyl, C₁-C₄ alkoxy or C₁-C₄ haloalkoxy; each R^(9a) is independently halogen, cyano, C₁-C₄ alkyl, C₁-C₄ haloalkyl, C₁-C₄ alkoxy or C₁-C₄ haloalkoxy; each R^(9b) is independently H, C₁-C₃ alkyl, C₁-C₃ alkylcarbonyl, C₁-C₃ alkoxy or C₁-C₃ alkoxycarbonyl; and each n is independently 0, 1 or 2; and a and b are independently 0, 1 or 2, provided that the sum of a and b is 1 or 2; and provided that when R¹ is Cl; and A is —C(═O)CH₂CH₂CF₃; then R² is other than Br or cyano.
 2. The compound of claim 1 wherein A is C₂-C₈ alkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl, C₂-C₈ haloalkyl, C₂-C₆ haloalkenyl, C₂-C₆ haloalkynyl, C₃-C₆ cycloalkyl, C₃-C₆ halocycloalkyl, C₄-C₈ alkylcycloalkyl, C₄-C₈ cycloalkylalkyl, C₂-C₆ alkoxyalkyl, C₂-C₆ haloalkoxyalkyl, C₂-C₆ alkoxyhaloalkyl, C₄-C₈ cycloalkoxyalkyl, C₂-C₆ cyanoalkyl, C₃-C₇ cyanoalkoxyalkyl, C₂-C₆ alkylthioalkyl, C₂-C₆ haloalkylthioalkyl, C₃-C₆ cycloalkylthioalkyl, C₂-C₆ alkylsulfonylalkyl or C₂-C₆ haloalkylsulfonylalkyl.
 3. The compound of claim 2 wherein A is C₂-C₈ alkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl, C₂-C₈ haloalkyl, C₂-C₆ haloalkenyl, C₂-C₆ haloalkynyl, C₃-C₆ cycloalkyl, C₃-C₆ halocycloalkyl, C₄-C₈ alkylcycloalkyl, C₄-C₈ cycloalkylalkyl, C₂-C₆ alkoxyalkyl, C₂-C₆ haloalkoxyalkyl or C₂-C₆ alkoxyhaloalkyl.
 4. The compound of claim 3 wherein A is C₂-C₈ alkyl, C₂-C₈ haloalkyl, C₂-C₆ haloalkenyl, C₂-C₆ alkoxyalkyl, C₂-C₆ haloalkoxyalkyl or C₂-C₆ alkoxyhaloalkyl; R¹ is halogen; and R² is halogen or cyano.
 5. The compound of claim 1 selected from the group consisting of 2-[3-bromo-2-(butoxy)phenoxy]-5-chloropyrimidine, 3-[(5-chloro-2-pyrimidinyl)oxy]-2-[[(2E)-4,4,4-trifluoro-2-buten-1-yl ]oxy]benzonitrile, 2-[3-bromo-2-(2,2,3,3-tetrafluoropropoxy)phenoxy]-5-chloropyrimidine, 3-[(5-chloro-2-pyrimidinyl)oxy]-2-(2,2,3,3,3-pentafluoropropoxy)benzonitrile, 2-butoxy-3-[(5-chloro-2-pyrimidinyl)oxy]benzonitrile, 3-[(5-chloro-2-pyrimidinyl)oxy]-2-(3,3,3-trifluoropropoxy)benzonitrile, 3-[(5-fluoro-2-pyrimidinyl)oxy]-2-(4,4,4-trifluorobutoxy)benzonitrile and 3-[(5-chloro-2-pyrimidinyl)oxy]-2-(4,4,4-trifluorobutoxy)benzonitrile.
 6. A herbicidal composition comprising a compound of claim 1 and at least one component selected from the group consisting of surfactants, solid diluents and liquid diluents.
 7. A herbicidal composition comprising a compound of claim 1, at least one active ingredient selected from the group consisting of other herbicides and herbicide safeners, and at least one component selected from the group consisting of surfactants, solid diluents and liquid diluents.
 8. A method for controlling the growth of undesired vegetation comprising contacting the vegetation or its environment with a herbicidally effective amount of a compound of claim
 1. 9. The compound of claim 1 wherein A is C₂-C₈ alkyl, C₂-C₈ haloalkyl, C₂-C₆ haloalkenyl, C₂-C₆ alkoxyalkyl, C₂-C₆ haloalkoxyalkyl or C₂-C₆ alkoxyhaloalkyl; R¹ is halogen; R² is cyano.
 10. The compound of claim 9 wherein A is C₂-C₈ haloalkyl or C₂-C₆ haloalkenyl.
 11. A herbicidal mixture comprising (a) a compound selected from Formula 1, N-oxides and salts thereof,

wherein A is C₂-C₈ alkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl, C₂-C₈ haloalkyl, C₂-C₆ haloalkenyl, C₂-C₆ haloalkynyl, C₃-C₆ cycloalkyl, C₃-C₆ halocycloalkyl, C₄-C₈ alkylcycloalkyl, C₄-C₈ cycloalkylalkyl, C₂-C₆ alkoxyalkyl, C₂-C₆ haloalkoxyalkyl, C₂-C₆ alkoxyhaloalkyl, C₄-C₈ cycloalkoxyalkyl, C₂-C₆ cyanoalkyl, C₃-C₇ cyanoalkoxyalkyl, C₁-C₆ nitroalkyl, C₂-C₆ alkylthioalkyl, C₂-C₆ haloalkylthioalkyl, C₃-C₈ cycloalkylthioalkyl, C₂-C₆ alkylsulfinylalkyl, C₂-C₆ haloalkylsulfinylalkyl, C₂-C₆ alkylsulfonylalkyl, C₂-C₆ haloalkylsulfonylalkyl, C₂-C₆ alkylcarbonyl, C₂-C₆ haloalkylcarbonyl, C₂-C₆ alkylcarbonylalkyl, C₂-C₆ haloalkylcarbonylalkyl, C₂-C₆ alkoxycarbonylalkyl, C₂-C₆ haloalkoxycarbonylalkyl or C₂-C₆ alkoxyalkylcarbonyl; or G; or C₁-C₄ alkyl substituted with Q; R¹ is halogen, C₁-C₄ alkyl, C₁-C₄ haloalkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl, C₁-C₄ alkoxy or S(O)_(n)R⁴; R² is halogen, cyano, nitro, CHO, C(═O)NH₂, C(═S)NH₂, SO₂NH₂, C₁-C₄ alkyl, C₂-C₄ alkenyl, C₂-C₄ alkynyl, C₁-C₄ haloalkyl, C₂-C₄ haloalkenyl, C₂-C₄ haloalkynyl, C₃-C₆ cycloalkyl, C₃-C₆ halocycloalkyl, C₄-C₈ alkylcycloalkyl, C₄-C₈ cycloalkylalkyl, C₂-C₆ alkylcarbonyl, C₂-C₆ haloalkylcarbonyl, C₂-C₆ alkoxycarbonyl, C₃-C₇ cycloalkylcarbonyl, C₂-C₄ alkoxy, C₃-C₄ alkenyloxy, C₃-C₄ alkynyloxy, C₁-C₄ haloalkoxy, C₃-C₆ cycloalkoxy, C₃-C₆ halocycloalkoxy, C₄-C₈ cycloalkylalkoxy, C₂-C₆ alkoxyalkyl, C₂-C₆ haloalkoxyalkyl, C₂-C₆ alkoxyhaloalkyl, C₂-C₆ alkoxyalkoxy, C₂-C₄ alkylcarbonyloxy, C₂-C₆ cyanoalkyl, C₂-C₆ cyanoalkoxy, C₂-C₄ alkylthioalkyl, C(═O)N(R^(5a))(R^(5b)), C(═NOR⁶)H, C(═NR⁷)H or SO_(n)R⁴; R³ is H or F; G is a 3- to 7-membered nonaromatic heterocyclic ring containing ring members selected from carbon, up to 4 heteroatoms selected from up to 2 O, up to 2 S and up to 4 N, and up to 3 ring members selected from C(═O), C(═S) and S(═O)_(a)(═NR⁶)_(b) and substituted with up to 3 substituents independently selected from halogen, cyano, C₁-C₄ alkyl, C₁-C₄ haloalkyl, C₁-C₄ alkoxy or C₁-C₄ haloalkoxy; Q is a phenyl ring optionally substituted with up to 5 substituents independently selected from R⁸; or a 5- or 6-membered heteroaromatic ring containing ring members selected from carbon atoms and up to 4 heteroatoms independently selected from up to 2 O, up to 2 S and up to 4 N atoms and optionally substituted with up to 3 substituents independently selected from R^(9a) on carbon atom ring members and R^(9b) on nitrogen atom ring members; each R⁴ is independently C₁-C₆ alkyl or C₁-C₆ haloalkyl; each R^(5a) is independently C₁-C₄ alkyl or C₁-C₄ haloalkyl; each R^(5b) is independently H, C₁-C₄ alkyl or C₁-C₄ haloalkyl; each R⁶ is independently H or C₁-C₄ alkyl; each R⁷ is independently H, amino, C₁-C₄ alkyl or C₁-C₄ alkylamino; each R⁸ is independently halogen, cyano, C₁-C₄ alkyl, C₁-C₄ haloalkyl, C₁-C₄ alkoxy or C₁-C₄ haloalkoxy; each R^(9a) is independently halogen, cyano, C₁-C₄ alkyl, C₁-C₄ haloalkyl, C₁-C₄ alkoxy or C₁-C₄ haloalkoxy; each R^(9b) is independently H, C₁-C₃ alkyl, C₁-C₃ alkylcarbonyl, C₁-C₃alkoxy or C₁-C₃ alkoxycarbonyl; each n is independently 0, 1 or 2; and a and b are independently 0, 1 or 2, provided that the sum of a and b is 1 or 2; and provided that when R¹ is Cl; R³ is H; and A is —C(═O)CH₂CH₂CF₃; then R² is other than Br or cyano; and (b) at least one active ingredient selected from (b1) photosystem II inhibitors, (b2) acetohydroxy acid synthase (AHAS) inhibitors, (b3) acetyl-CoA carboxylase (ACCase) inhibitors, (b4) auxin mimics, (b5) 5-enol-pyruvylshikimate-3-phosphate (EPSP) synthase inhibitors, (b6) photosystem I electron diverters, (b7) protoporphyrinogen oxidase (PPO) inhibitors, (b8) glutamine synthetase (GS) inhibitors, (b9) very long chain fatty acid (VLCFA) elongase inhibitors, (b10) auxin transport inhibitors, (b11) phytoene desaturase (PDS) inhibitors, (b12) 4-hydroxyphenyl-pyruvate dioxygenase (HPPD) inhibitors, (b13) homogentisate solenesyltransererase (HST) inhibitors, (b14) cellulose biosynthesis inhibitors, (b15) other herbicides including mitotic disruptors, organic arsenicals, asulam, bromobutide, cinmethylin, cumyluron, dazomet, difenzoquat, dymron, etobenzanid, flurenol, fosamine, fosamine-ammonium, hydantocidin, metam, methyldymron, oleic acid, oxaziclomefone, pelargonic acid and pyributicarb, (b16) herbicide safeners, and salts of compounds of (b1) through (b16).
 12. The herbicidal mixture of claim 11, wherein the at least one active ingredient is selected from (1) photosystem II inhibitors, (b2) acetohydroxy acid synthase (AHAS) inhibitors, (b4) auxin mimics, (b5) 5-enol-pyruvylshikimate-3-phosphate (EPSP) synthase inhibitors, (b7) protoporphyrinogen oxidase (PPO) inhibitors, (b9) very long chain fatty acid (VLCFA) elongase inhibitors and (b12) 4-hydroxyphenyl-pyruvate dioxygenase (HPPD) inhibitors.
 13. The herbicidal mixture of claim 11, wherein the at least one active ingredient (b) is selected from the group consisting of 2,4-D, acetochlor, alachlor, atrazine, bromoxynil, bentazon, bicyclopyrone, carfentrazone-ethyl, cloransulam-methyl, dicamba, dimethenamid-p, florasulam, flufenacet, flumioxazin, flupyrsulfuron-methyl, fluroxypyr-meptyl, glyphosate, halauxifen-methyl, isoxaflutole, MCPA, mesotrione, metolachlor, metsulfuron-methyl, nicosulfuron, pyrasulfotole, pyroxasulfone, pyroxsulam, rimsulfuron, saflufenacil, tembotrione, thifensulfuron-methyl, topramazone and tribenuron.
 14. The herbicidal mixture of claim 11, wherein A is C₂- C₈ alkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl, C₂- C₈ haloalkyl, C₂-C₆ haloalkenyl, C₂-C₆ haloalkynyl, C₃-C₆ cycloalkyl, C₃-C₆ halocycloalkyl, C₄- C₈ alkylcycloalkyl, C₄- C₈ cycloalkylalkyl, C₂-C₆ alkoxyalkyl, C₂-C₆ haloalkoxyalkyl, C₂-C₆ alkoxyhaloalkyl, C₄- C₈ cycloalkoxyalkyl, C₂-C₆ cyanoalkyl, C₃-C₇ cyanoalkoxyalkyl, C₂-C₆ alkylthioalkyl, C₂-C₆ haloalkylthioalkyl, C₃-C₈ cycloalkylthioalkyl, C₂-C₆ alkylsulfonylalkyl or C₂-C₆ haloalkylsulfonylalkyl; R¹ is halogen, C₁-C₄ alkyl or C₁-C₄ haloalkyl; R² is halogen, cyano, CHO, C₁-C₄ alkyl, C₂-C₄ alkenyl, C₂-C₄ alkynyl, C₁-C₄ haloalkyl, C₂-C₄ haloalkenyl, C₂-C₄ haloalkynyl, C₃-C₆ cycloalkyl, C₃-C₆ halocycloalkyl, C₂-C₆ alkylcarbonyl, C₂-C₆ haloalkylcarbonyl, C₂-C₆ alkoxycarbonyl, C₁-C₄ alkoxy, C₁-C₄ haloalkoxy, C₂-C₆ alkoxyalkyl, C₂-C₆ haloalkoxyalkyl, C₂-C₆ cyanoalkyl or SO_(n)R⁴; and R³ is H.
 15. The herbicidal mixture of claim 14 wherein A is C₂- C₈ alkyl, C₂- C₈ haloalkyl, C₂-C₆ haloalkenyl, C₂-C₆ alkoxyalkyl, C₂-C₆ haloalkoxyalkyl or C₂-C₆ alkoxyhaloalkyl; R¹ is halogen; R² is cyano.
 16. The herbicidal mixture of claim 15 wherein A is C₂-C₈ haloalkyl or C₂-C₆ haloalkenyl.
 17. A method for controlling the growth of undesired vegetation in a crop of genetically modified plants that exhibit traits of glyphosate tolerance, glufosinate tolerance, ALS herbicide tolerance, dicamba tolerance, imidazolinone herbicide tolerance, 2,4-D tolerance, HPPD tolerance and mesotrione tolerance, comprising contacting the vegetation or its environment with a herbicidally effective amount of a compound selected from Formula 1, N-oxides and salts thereof,

wherein A is C₂-C₈ alkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl, C₂-C₈ haloalkyl, C₂-C₆ haloalkenyl, C₂-C₆ haloalkynyl, C₃-C₆ cycloalkyl, C₃-C₆ halocycloalkyl, C₄-C₈ alkylcycloalkyl, C₄-C₈ cycloalkylalkyl, C₂-C₆ alkoxyalkyl, C₂-C₆ haloalkoxyalkyl, C₂-C₆ alkoxyhaloalkyl, C₄-C₈ cycloalkoxyalkyl, C₂-C₆ cyanoalkyl, C₃-C₇ cyanoalkoxyalkyl, C₁-C₆ nitroalkyl, C₂-C₆ alkylthioalkyl, C₂-C₆ haloalkylthioalkyl, C₃-C₈ cycloalkylthioalkyl, C₂-C₆ alkylsulfinylalkyl, C₂-C₆ haloalkylsulfinylalkyl, C₂-C₆ alkylsulfonylalkyl, C₂-C₆ haloalkylsulfonylalkyl, C₂-C₆ alkylcarbonyl, C₂-C₆ haloalkylcarbonyl, C₂-C₆ alkylcarbonylalkyl, C₂-C₆ haloalkylcarbonylalkyl, C₂-C₆ alkoxycarbonylalkyl, C₂-C₆ haloalkoxycarbonylalkyl or C₂-C₆ alkoxyalkylcarbonyl; or G; or C₁-C₄ alkyl substituted with Q; R¹ is halogen, C₁-C₄ alkyl, C₁-C₄ haloalkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl, C₁-C₄ alkoxy or S(O)_(n)R⁴; R² is halogen, cyano, nitro, CHO, C(═O)NH₂, C(═S)NH₂, SO₂NH₂, C₁-C₄ alkyl, C₂-C₄ alkenyl, C₂-C₄ alkynyl, C₁-C₄ haloalkyl, C₂-C₄ haloalkenyl, C₂-C₄ haloalkynyl, C₃-C₆ cycloalkyl, C₃-C₆ halocycloalkyl, C₄-C₈ alkylcycloalkyl, C₄-C₈ cycloalkylalkyl, C₂-C₆ alkylcarbonyl, C₂-C₆ haloalkylcarbonyl, C₂-C₆ alkoxycarbonyl, C₃-C₇ cycloalkylcarbonyl, C₂-C₄ alkoxy, C₃-C₄ alkenyloxy, C₃-C₄ alkynyloxy, C₁-C₄ haloalkoxy, C₃-C₆ cycloalkoxy, C₃-C₆ halocycloalkoxy, C₄-C₈ cycloalkylalkoxy, C₂-C₆ alkoxyalkyl, C₂-C₆ haloalkoxyalkyl, C₂-C₆ alkoxyhaloalkyl, C₂-C₆ alkoxyalkoxy, C₂-C₄ alkylcarbonyloxy, C₂-C₆ cyanoalkyl, C₂-C₆ cyanoalkoxy, C₂-C₄ alkylthioalkyl, C(═O)N(R^(5a))(R^(5b)), C(═NOR⁶)H, C(═NR⁷)H or SO_(n)R⁴; R³ is H or F; G is a 3- to 7-membered nonaromatic heterocyclic ring containing ring members selected from carbon, up to 4 heteroatoms selected from up to 2 O, up to 2 S and up to 4 N, and up to 3 ring members selected from C(═O), C(═S) and S(═O)_(a)(═NR⁶)_(b) and substituted with up to 3 substituents independently selected from halogen, cyano, C₁-C₄ alkyl, C₁-C₄ haloalkyl, C₁-C₄ alkoxy or C₁-C₄ haloalkoxy; Q is a phenyl ring optionally substituted with up to 5 substituents independently selected from R⁸; or a 5- or 6-membered heteroaromatic ring containing ring members selected from carbon atoms and up to 4 heteroatoms independently selected from up to 2 O, up to 2 S and up to 4 N atoms and optionally substituted with up to 3 substituents independently selected from R^(9a) on carbon atom ring members and R^(9b) on nitrogen atom ring members; each R⁴ is independently C₁-C₆ alkyl or C₁-C₆ haloalkyl; each R^(5a) is independently C₁-C₄ alkyl or C₁-C₄ haloalkyl; each R^(5b) is independently H, C₁-C₄ alkyl or C₁-C₄ haloalkyl; each R⁶ is independently H or C₁-C₄ alkyl; each R⁷ is independently H, amino, C₁-C₄ alkyl or C₁-C₄ alkylamino; each R⁸ is independently halogen, cyano, C₁-C₄ alkyl, C₁-C₄ haloalkyl, C₁-C₄ alkoxy or C₁-C₄ haloalkoxy; each R^(9a) is independently halogen, cyano, C₁-C₄ alkyl, C₁-C₄ haloalkyl, C₁-C₄ alkoxy or C₁-C₄ haloalkoxy; each R^(9b) is independently H, C₁-C₃ alkyl, C₁-C₃ alkylcarbonyl, C₁-C₃ alkoxy or C₁-C₃ alkoxycarbonyl; each n is independently 0, 1 or 2; and a and b are independently 0, 1 or 2, provided that the sum of a and b is 1 or 2; and provided that when R¹ is Cl; R³ is H; and A is —C(═O)CH₂CH₂CF₃; then R² is other than Br or cyano.
 18. The method of claim 17, wherein A is C₂- C₈ alkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl, C₂- C₈ haloalkyl, C₂-C₆ haloalkenyl, C₂-C₆ haloalkynyl, C₃-C₆ cycloalkyl, C₃-C₆ halocycloalkyl, C₄- C₈ alkylcycloalkyl, C₄- C₈ cycloalkylalkyl, C₂-C₆ alkoxyalkyl, C₂-C₆ haloalkoxyalkyl, C₂-C₆ alkoxyhaloalkyl, C₄- C₈ cycloalkoxyalkyl, C₂-C₆ cyanoalkyl, C₃-C₇ cyanoalkoxyalkyl, C₂-C₆ alkylthioalkyl, C₂-C₆ haloalkylthioalkyl, C₃-C₈ cycloalkylthioalkyl, C₂-C₆ alkylsulfonylalkyl or C₂-C₆ haloalkylsulfonylalkyl; R¹ is halogen, C₁-C₄ alkyl or C₁-C₄ haloalkyl; R² is halogen, cyano, CHO, C₁-C₄ alkyl, C₂-C₄ alkenyl, C₂-C₄ alkynyl, C₁-C₄ haloalkyl, C₂-C₄ haloalkenyl, C₂-C₄ haloalkynyl, C₃-C₆ cycloalkyl, C₃-C₆ halocycloalkyl, C₂-C₆ alkylcarbonyl, C₂-C₆ haloalkylcarbonyl, C₂-C₆ alkoxycarbonyl, C₁-C₄ alkoxy, C₁-C₄ haloalkoxy, C₂-C₆ alkoxyalkyl, C₂-C₆ haloalkoxyalkyl, C₂-C₆ cyanoalkyl or SO_(n)R⁴; and R³ is H.
 19. The method of claim 18 wherein A is C₂- C₈ alkyl, C₂- C₈ haloalkyl, C₂-C₆ haloalkenyl, C₂-C₆ alkoxyalkyl, C₂-C₆ haloalkoxyalkyl or C₂-C₆ alkoxyhaloalkyl; R¹ is halogen; R² is cyano.
 20. The method of claim 19 wherein A is C₂-C₈ haloalkyl or C₂-C₆ haloalkenyl. 